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Chemical Structure| 126-33-0 Chemical Structure| 126-33-0

Structure of Sulfolane
CAS No.: 126-33-0

Chemical Structure| 126-33-0

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Product Details of [ 126-33-0 ]

CAS No. :126-33-0
Formula : C4H8O2S
M.W : 120.17
SMILES Code : O=S1(CCCC1)=O
MDL No. :MFCD00005484
InChI Key :HXJUTPCZVOIRIF-UHFFFAOYSA-N
Pubchem ID :31347

Safety of [ 126-33-0 ]

GHS Pictogram:
Signal Word:Warning
Hazard Statements:H302
Precautionary Statements:P264-P270-P301+P312-P330-P501

Computational Chemistry of [ 126-33-0 ] Show Less

Physicochemical Properties

Num. heavy atoms 7
Num. arom. heavy atoms 0
Fraction Csp3 1.0
Num. rotatable bonds 0
Num. H-bond acceptors 2.0
Num. H-bond donors 0.0
Molar Refractivity 28.19
TPSA ?

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

42.52 Ų

Lipophilicity

Log Po/w (iLOGP)?

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

0.88
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

-0.77
Log Po/w (WLOGP)?

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

1.28
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.

-0.01
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

0.97
Consensus Log Po/w?

Consensus Log Po/w: Average of all five predictions

0.47

Water Solubility

Log S (ESOL):?

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

-0.1
Solubility 95.5 mg/ml ; 0.794 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.

0.35
Solubility 272.0 mg/ml ; 2.26 mol/l
Class?

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

Highly 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

-0.86
Solubility 16.4 mg/ml ; 0.136 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

No
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.

-7.58 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

2.0
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)

2.37

Application In Synthesis of [ 126-33-0 ]

* 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 [ 126-33-0 ]

[ 126-33-0 ] Synthesis Path-Downstream   1~55

  • 1
  • [ 110-01-0 ]
  • [ 126-33-0 ]
YieldReaction ConditionsOperation in experiment
98% With oxone; diethylamine; In water; acetonitrile; at 20℃; for 0.0833333h; General procedure: To a well-stirred solution of thioether (1 mmol) and diethylamine (0.2 mmol) in acetonitrile (2 mL) was added the solution of Oxone (1.5 mmol) in water(4 mL). Stirring was continued and the reaction was monitored by TLC. Uponcompletion of the reaction, the mixture was diluted with chilled water. In most of the cases, sulfones were obtained as pure solid products. Thus, they were isolated by simple filtration. However, when the resulting sulfone was a liquid,the product was extracted with ethyl acetate. The organic extract was washedwith water, dried over anhydrous sodium sulfate, and the solvent was removed.The resultant residue on filtration through a short column of silica gel afforded pure sulfone.
97% With 3-butyl-1-methyl-1H-imidazolium perrhenate; dihydrogen peroxide; 1-butyl-3-methylimidazolium Tetrafluoroborate; In water; at 60℃; for 1h;Schlenk technique; Inert atmosphere; Green chemistry; General procedure: To a stirred solution of sulfide (10mmol) and [C4mim][ReO4] (0.1955g, 5 mol%) in [C4mim][BF4] (2mL), an aqueous solution of hydrogen peroxide (35% in water) (3.5mL, 40mmol) is added in 2-3 portions at 60C. The progress of the reaction is followed by TLC. The reaction mixture is extracted with diethyl ether (5×10mL) and the extract is dried over anhydrous MgSO4. The yield and selectivity of methyl phenyl sulfone are calculated from calibration curves (r2>0.999) recorded using 3-methylanisole and 1,4-diacetylbenzene as internal standard. The crude product is obtained by rolling evaporation and purified by column chromatography separation (silica gel using hexane/ethyl acetate 90:10 v/v). The RTIL phase is diluted with CH2Cl2 and then treated with MnO2 to destroy the excess peroxide. The obtained liquid is first dried over anhydrous MgSO4 and then for 4h in vacuo at 50C to remove CH2Cl2. Fresh substrate and hydrogen peroxide are then added for a new reaction cycle. All products are characterized by melting point, 1H NMR, 13C NMR and IR spectroscopy (see Supporting information).
96% With sodium hypochlorite;isocyanuric acid; In water; toluene; at 20℃; for 1h; (Example 13) Tetrahydrothiophene (1.00 g, 11.3 mmol) and cyanuric acid (146 mg, 1.13 mmol) were mixed with toluene (20 mL). 10% aqueous solution of sodium hypochlorite (19.3 g, 26.0 mmol) was added to the mixture at room temperature, and it was stirred for 1 hour. After that, sodium sulfite (712 mg, 5.65 mmol) was added to the reaction mixture, and it was extracted with ethyl acetate (10 mL). An aqueous layer was extracted with ethyl acetate (10 mL) 5 times, and a combined organic layer was concentrated under reduced pressure. The residue was subjected to purification by means of a silica gel column to obtain tetrahydrothiophene 1,1-dioxide (1.31 g, yield: 96%). 1H-NMR (300MHz, CDCl3) delta 2.13-2.30 (4H, m), 2.95-3.07 (4H, m)
94% With (pyridinium)H3PMo11VO40; dihydrogen peroxide; In water; acetonitrile; at 40℃; for 2.5h; General procedure: The oxidation of methyl phenyl sulfide to methyl phenyl sulfoxide or methyl phenyl sulfone (Scheme 1) was typically carried out bystirring a solution of 0.7 mmol of the substrate and 0.01 mmol of the catalyst in 5 mL of acetonitrile, at 20 or 40 C, respectively. Theoxidant used was H2O2 35% in aqueous solution (2 or 20 mmol,respectively). The sample was collected from the reaction mixtureduring the reaction at time intervals. About 20 muL of the reactionmixture was taken for each sample, which was then diluted in amixture of water-dichloromethane (2 mL). The dichloromethanelayer was dried with anhydrous sodium sulfate and filtered. GC/MSanalyses were performed on an HP 5971 mass detector coupled to anHP gas chromatograph fitted with a 30 m×0.25 mm DB5 capillarycolumn. The percentages of each compound in the reaction mixturewere directly estimated from the corresponding chromatographicpeak areas. The yield (%) of pure sulfoxide or sulfone, the turnovernumber (TON: product mol×catalyst mol-1) and turnover frequency(TOF: product mol×catalyst mol-1×h-1) were also calculated. Under these optimum conditions and using M11PV1Py1 ascatalyst, different sulfides were oxidized to sulfoxides (for 30 min)and to sulfones (for 2.5 and 3.5 h) depending on the substrate.
92% With 1,3,5-trichloro-2,4,6-triazine; dihydrogen peroxide; In water; acetonitrile; at 20℃; for 0.25h; General procedure: To a mixture of sulfide (1 mmol) and TCT (1 mmol, 0.184 g) in acetonitrile (5 mL) was added 30% H2O2 (2 mmol, 0.2 mL). The mixture was stirred at room temperature for the appropriate period of time until complete consumption of the starting material as observed by TLC. After completion of the reaction, H2O (10 mL) was added to the reaction mixture which was then extracted with EtOAc (4 × 5 mL) and the combined extracts were dried (MgSO4). The filtrate was evaporated and the corresponding sulfone was obtained as the only product (Table 1).
92% With Octanoic acid; dihydrogen peroxide; In acetonitrile; at 50℃; for 0.416667h;Schlenk technique; Green chemistry; General procedure: An oven-dried Schlenk flask was allowed to cool toroom temperature and charged sequentially with sulfide(1.0 mmol), MeCN (3.0 mL) and caprylic acid (20 mol%).The reaction was then activated by the addition of 30%H2O2 (2.4 equiv.) and stirred at 50 C for the required timeas given in Table 4. The progress of reaction was monitoredby GC. After completion of the reaction, the reaction to the reaction mixture. Then the product was extractedwith CH2Cl2 (30 mL) and then washed with distilled water(10 mL). The organic extract dried over Na2SO4 and thesolvent removed under reduced pressure. The resultantproduct was purified (if necessary) by column chromatographyusing silica gel (60-120 mesh) with n-hexaneand ethyl acetate as solvent to get the pure product. Thestructure of the product was confirmed by GC-MS, M.P./B.P. and 1H NMR spectroscopic techniques.
92% With 2,2,2-Trifluoroacetophenone; dihydrogen peroxide; acetonitrile; In tert-butyl alcohol; at 20℃; for 3h;pH 11;Green chemistry; General procedure: Sulfide (1.00 mmol) was placed in a round-bottom flask, followed by t-BuOH (0.5 mL), 2,2,2-trifluoroacetophenone (34.8 mg, 0.20 mmol), aq buffer solution (0.5 mL, 0.6 M K2CO3/4 × 10-4 M EDTA disodium salt), MeCN (0.15 mL, 3.00 mmol) and 30% aq H2O2 (0.36 mL, 3.00 mmol). The reaction mixture was stirred for 1-5 h. The reaction was quenched with 1 M HCl (5 mL) and extracted with CHCl3 (3 × 10 mL). The combined organic layers were dried over Na2SO4, filtered and concentrated in vacuo to afford the desired product.
86% With anthracene; oxygen; acetic acid; In isopropyl alcohol; at 75℃; for 3h;Irradiation; General procedure: In the internal irradiation type photochemical reaction apparatus 4, 0.37 g (6 mmol) of dimethyl sulfide,Anthracene 0.21 g (1.2 mmol,20 mol% of dimethylsulfide) was dissolved in 75 mL of 2-propanol and 25 mL of acetic acid and stored.While supplying oxygen as Ultrafine bubbles at 5 C./minute at 75 C.,Light was irradiated by immersing the light source in the reaction solution.5 g of Amberlyst 15 (manufactured by Organo Corporation) was packed in the solid acid catalyst layer 6, placed in a circulation path before entering the reaction vessel,So that the organic acid in the reaction solution is brought into contact with the solid acid catalyst.The reaction solution was circulated for 2 hours while supplying Ultrafine bubble-form oxygen, and the raw material dimethylsulfide disappeared. The yield of dimethyl sulfone (DMSO 2) was analyzed by gas chromatography.The results are shown in Table 1.
With tetrabutylammonium polychromiumphosphotungstate trihydrate; dihydrogen peroxide; In water; acetonitrile; at 25℃; for 0.166667h;Green chemistry; General procedure: PWCr catalyst (0.0245 mmol), CH3CN (3 mL), sulfide (1 mmol), and hydrogenperoxide (4 mmol, 30% aq solution) were added to a glass tube as the reaction vessel. The reaction was carried out at 298 K. The mixture was sampled periodically and analyzed by GC. After completion of the reaction, the product was extracted with CH2Cl2 and the combined organic layers were dried over anhydrous Na2SO4. The solvent was removed under reduced pressure to give the corresponding pure sulfone. The products were identified by comparison of their 1H NMR and 13C NMR signals with the literature data (see Supplementary Data, Figures S5-S18).
With dihydrogen peroxide; In water; acetonitrile; at 50℃; General procedure: A solution of sulfide (1 mmol) and catalyst (100 mg), in acetonitrile (9 mL), was added to H2O2 35% (w/v) (10 mmol). The mixture was stirred at 50 C for a time period (see Tables 1 and 2). The solvent was evaporated and then H2O (5 mL) was added. The substrate was extracted with toluene (2 × mL) and dried with anhydrous Na2SO4; filtration and evaporation afforded the corresponding sulfoxides. The crude solids were purified by recrystallization to affordthe pure sulfones
With bis(N-tert-butylsalicylaldiminato)zinc(II); dihydrogen peroxide; In water; at 50℃; for 3.15h;Green chemistry; General procedure: To a mixture of the sulfide (1 mmol) and 30 % H2O2 (2 mmol), the catalyst (1 mmol) was added and the mixture was stirred at 50 C for a specified time. The progress of the reaction was monitored by TLC (petroleum ether/ethylacetate 8:3) and GC. After completion of the reaction, the product was extracted with ethyl acetate and the catalyst was separated by filtration. The combined organics were washed with brine (5 ml) and dried over anhydrous Na2SO4. Further purification was achieved by short-column chromatography on silica gel with EtOAc/n-hexane as the eluent.
With bis(N-isopropylsalicylaldiminato)oxovanadium(IV); dihydrogen peroxide; In neat (no solvent); at 45℃; for 1.08333h;Green chemistry; General procedure: To a mixture of the sulfide (1mmol) and 30% H2O2 (1.5mmol), the catalyst (0.01mmol) was added and the mixture was stirred at 45C for a specified time. The progress of the reaction was monitored by TLC (petroleum ether/ethylacetate 8:3) and GC. After completion of the reaction, the product was extracted with ethyl acetate and the catalyst was separated by filtration. The combined organics were washed with brine (5ml) and dried over anhydrous Na2SO4. Further purification was achieved by short-column chromatography on silica gel with EtOAc/n-hexane as the eluent
With C30H22Cl4N4O2Pd2; dihydrogen peroxide; In acetonitrile; at 50℃; for 4.15h; General procedure: A mixture of 1 mmol sulfide and H2O2 (3 mmol) wasadded to a stirring solution of CoL(NO3)2 (1), NiLCl2 (2),ZnL(NO3)2 (3) and Pd2LCl4 (4) Schiff base complexes(0.01 mmol) in acetonitrile (3 ml) at 50 C for the requiredperiod of time (4 h). After completion of the reaction (TLC),the catalyst was separated by filtration, washed three timeswith acetonitrile and then dried under vacuum and usedfor the next oxidation cycle. The products were analyzed byGC using diphenyl sulfide as the internal standard.
With 4C16H36N(1+)*PW11CrO39(4-)*3H2O; dihydrogen peroxide; In water; at 25℃; for 0.166667h;Green chemistry; General procedure for the oxidation of sulfides to sulfones: The sulfide (1mmol) was added to a solution of 30% H2O2 (6.5 equiv) and TBAPWCr (16.5mumol), and the mixture was stirred at room temperature for the time specified in Table2. The progress of reactions was monitored by TLC and GC. After completion of the reaction, the product was extracted with ethyl acetate. Further purification was achieved by short-column chromatography on silica gel with EtOAc/n-hexane (1/10) as eluent. All of the products were known and characterized by 1HNMR and 13CNMR (see Supplementary data, Figs. S3-S15) [38-41].

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  • 2
  • [ 77-79-2 ]
  • [ 126-33-0 ]
YieldReaction ConditionsOperation in experiment
With hydrogen;Raney nickel; In water; at 35℃; under 7500.75 Torr; for 1.3h;Product distribution / selectivity; An amount of 0.186 g (1.0 mmol) of ferrocene was fed into a 500-mL stainless autoclave equipped with a stirrer, a thermometer, a pressure gauge, and a heater. Then, 77 g of sulfur dioxide was charged therein. Next, the autoclave was heated to 100C and 54 g (1.0 mol) of 1, 3-butadiene was injected thereto at a rate of 0.38 g/min using a pump. The mixture was stirred for one hour at 100C. During the stirring, the pressure inside the autoclave was 2.7 to 0.7 MPa. After the pressure inside the autoclave was discharged, 150 g of water was added and the autoclave was cooled to 60C. The autoclave contents were filtered through a filter paper to give a 3-sulfolene aqueous solution. The amount of 3-sulfolene in the obtained aqueous solution was measured using liquid chromatography and the measurement was 103 g (0.87 mol). The yield from 1,3-butadiene was 87%. It is to be noted that polymers were not found on the filter paper used in filtering. All of the obtained 3-sulfolene aqueous solution was fed into a 500-ml conical flask and 70 g of water was added thereto. The solution was warmed to 35C and bubbled with air at a rate of 100 ml/min for one hour. In this manner, sulfur dioxide dissolved in the 3-sulfolene aqueous solution was removed. The concentration of sulfur dioxide in the 3-sulfolene aqueous solution was measured using ion chromatography and the measurement was 31 ppm. Next, 200 g of the obtained 3-sulfolene aqueous solution (3-sulfolene content of 64 g (0.54 mol)) and 1.04 g (0.52 g of pure nickel) of Raney nickel (water content of 50%) were fed into a 500-mL stainless autoclave equipped with a stirrer, a thermometer, a pressure gauge, and a heater. The temperature inside the autoclave was maintained at 35C. Hydrogen was introduced into the autoclave until the pressure gauge read 1.0 MPa. The reaction was initiated while the mixture was stirred at 1000 rpm. Hydrogen was consumed in the hydrogenation reaction and was additionally supplied, when the reading by the pressure gauge lowered to 0.9 MPa, to pressurize to 1.0 MPa. This operation was repeated until the pressure stopped lowering, at which the reaction was determined to be completed. As a result, the reaction time from the start to the completion of the reaction was 78 minutes. After the reaction completed, the reaction rate of hydrogenation was measured using gas chromatography. The measurement clarified that 3-sulfolene was vanished and the reaction was 100% progressed. Table 1 shows the measurements of the amount of generated polymers and the reaction time of hydrogenation.
  • 3
  • [ 126-33-0 ]
  • [ 23431-48-3 ]
  • [ 6628-06-4 ]
  • 4
  • [ 126-33-0 ]
  • [ 925-90-6 ]
  • [ 29325-66-4 ]
  • 5
  • [ 126-33-0 ]
  • [ 100-52-7 ]
  • [ 100-66-3 ]
  • [ 29866-60-2 ]
  • 6
  • [ 17200-23-6 ]
  • [ 126-33-0 ]
  • 7
  • [ 126-33-0 ]
  • [ 100-44-7 ]
  • [ 74-88-4 ]
  • [ 53292-12-9 ]
  • 9
  • [ 1600-44-8 ]
  • [ 126-33-0 ]
YieldReaction ConditionsOperation in experiment
3.14 - 83% With peroxynitrous acid; at 25℃; for 0.166667 - 4h;pH 7.4 - 12.7;phosphate buffer;Reactivity; Example 1. The corrole metal complexes prevent oxidation and nitration of small molecules by ROS and RNS. Table 1 summarizes the results obtained by treating five different molecules with peroxynitrite, with and without catalytic amounts of 1-Fe or 1-Mn. These particular molecules were specifically chosen because they represent targets of hydroxy 1 radical, nitrogen dioxide, and of oxygen transfer reagents. In addition, their reaction products are easily identified and quantified by established methods. The results were very illuminative: both complexes rescued the simple molecule DMSO, as well as the more sophisticated one, deoxyribose, from peroxynitrite-derived hydroxyl radical. The situation with regard to nitration by reactive nitrogen species originating from peroxynitrite was quite different: 1-Mn completely eliminated the reactions of both relevant molecules, while 1-Fe had no effect on the nitration of tyrosine, and was only partially effective in avoiding that of fluorescein. This is perfectly consistent with the mode of action of the complexes on peroxynitrite, as dilute nitrite obtained from 1-Mn (Scheme 2, equation 2) is not a nitrating agent while nitrate (from the action of 1-Fe, Scheme 2, equation 1) is. Both complexes were quite (but not absolutely) effective with regard to arresting the oxidation of tetramethylenesulfoxide to sulfone, in a way which is most likely an oxygen atom transfer reaction, with 1-Fe displaying some larger efficiency. Additional experiments were carried out by using CuSO4/ascorbate as the initiator of reactive oxygen species (by the complex Fenton-type oxidation that produces hydroxyl radical via the involvement of superoxide anion radical and <n="26"/>Hydrogen peroxide), as to bridge between the results of the small molecules and those obtained by oxidation of LDL. 1-Fe eliminated the oxidation of DMSO to malonaldehyde completely and 1-Mn did it only partially (65% inhibition), which is consistent with the faster decomposition of hydrogen peroxide by 1-Fe relative to 1- Mn.These investigations clearly point toward the following conclusions: a) both complexes serve very well for preventing the formation of hydroxyl radical from peroxynitrite; b) the iron complex is more efficient in avoiding the formation of metal-induced hydroxyl radical; c) the manganese complex is more efficient in inhibiting the formation of reactive nitrogen species from peroxynitrite.; (i) Oxidation of small molecules by peroxynitrite; c) Sulfolane from tetramethylene sulfoxide: Peroxynitrite (6 mM) was added to a solution of tetramethylene sulfoxide (0.038 mM) in phosphate buffer solution pH 7.4 and T= 25 0C, both in the presence and absence of 38 muM 1-Fe or 1-Mn. The sulfolane was extracted into diethyl ether after 10 min of stirring and quantified by GC analysis. The same experiment was done at pH 12.7, with a reaction time of 4 hr.
0.1 - 0.4% With peroxynitrous acid;[iron(III)(C19H6N2(C6F5)3(SO3H)2]; at 25℃; for 0.166667 - 4h;pH 7.4 - 12.7;phosphate buffer;Reactivity; Example 1. The corrole metal complexes prevent oxidation and nitration of small molecules by ROS and RNS. Table 1 summarizes the results obtained by treating five different molecules with peroxynitrite, with and without catalytic amounts of 1-Fe or 1-Mn. These particular molecules were specifically chosen because they represent targets of hydroxy 1 radical, nitrogen dioxide, and of oxygen transfer reagents. In addition, their reaction products are easily identified and quantified by established methods. The results were very illuminative: both complexes rescued the simple molecule DMSO, as well as the more sophisticated one, deoxyribose, from peroxynitrite-derived hydroxyl radical. The situation with regard to nitration by reactive nitrogen species originating from peroxynitrite was quite different: 1-Mn completely eliminated the reactions of both relevant molecules, while 1-Fe had no effect on the nitration of tyrosine, and was only partially effective in avoiding that of fluorescein. This is perfectly consistent with the mode of action of the complexes on peroxynitrite, as dilute nitrite obtained from 1-Mn (Scheme 2, equation 2) is not a nitrating agent while nitrate (from the action of 1-Fe, Scheme 2, equation 1) is. Both complexes were quite (but not absolutely) effective with regard to arresting the oxidation of tetramethylenesulfoxide to sulfone, in a way which is most likely an oxygen atom transfer reaction, with 1-Fe displaying some larger efficiency. Additional experiments were carried out by using CuSO4/ascorbate as the initiator of reactive oxygen species (by the complex Fenton-type oxidation that produces hydroxyl radical via the involvement of superoxide anion radical and <n="26"/>Hydrogen peroxide), as to bridge between the results of the small molecules and those obtained by oxidation of LDL. 1-Fe eliminated the oxidation of DMSO to malonaldehyde completely and 1-Mn did it only partially (65% inhibition), which is consistent with the faster decomposition of hydrogen peroxide by 1-Fe relative to 1- Mn.These investigations clearly point toward the following conclusions: a) both complexes serve very well for preventing the formation of hydroxyl radical from peroxynitrite; b) the iron complex is more efficient in avoiding the formation of metal-induced hydroxyl radical; c) the manganese complex is more efficient in inhibiting the formation of reactive nitrogen species from peroxynitrite.; (i) Oxidation of small molecules by peroxynitrite; c) Sulfolane from tetramethylene sulfoxide: Peroxynitrite (6 mM) was added to a solution of tetramethylene sulfoxide (0.038 mM) in phosphate buffer solution pH 7.4 and T= 25 0C, both in the presence and absence of 38 muM 1-Fe or 1-Mn. The sulfolane was extracted into diethyl ether after 10 min of stirring and quantified by GC analysis. The same experiment was done at pH 12.7, with a reaction time of 4 hr.
0.18 - 0.6% With peroxynitrous acid;[manganese(III)(C19H6N2(C6F5)3(SO3H)2]; at 25℃; for 0.166667 - 4h;pH 7.4 - 12.7;phosphate buffer;Reactivity; Example 1. The corrole metal complexes prevent oxidation and nitration of small molecules by ROS and RNS. Table 1 summarizes the results obtained by treating five different molecules with peroxynitrite, with and without catalytic amounts of 1-Fe or 1-Mn. These particular molecules were specifically chosen because they represent targets of hydroxy 1 radical, nitrogen dioxide, and of oxygen transfer reagents. In addition, their reaction products are easily identified and quantified by established methods. The results were very illuminative: both complexes rescued the simple molecule DMSO, as well as the more sophisticated one, deoxyribose, from peroxynitrite-derived hydroxyl radical. The situation with regard to nitration by reactive nitrogen species originating from peroxynitrite was quite different: 1-Mn completely eliminated the reactions of both relevant molecules, while 1-Fe had no effect on the nitration of tyrosine, and was only partially effective in avoiding that of fluorescein. This is perfectly consistent with the mode of action of the complexes on peroxynitrite, as dilute nitrite obtained from 1-Mn (Scheme 2, equation 2) is not a nitrating agent while nitrate (from the action of 1-Fe, Scheme 2, equation 1) is. Both complexes were quite (but not absolutely) effective with regard to arresting the oxidation of tetramethylenesulfoxide to sulfone, in a way which is most likely an oxygen atom transfer reaction, with 1-Fe displaying some larger efficiency. Additional experiments were carried out by using CuSO4/ascorbate as the initiator of reactive oxygen species (by the complex Fenton-type oxidation that produces hydroxyl radical via the involvement of superoxide anion radical and <n="26"/>Hydrogen peroxide), as to bridge between the results of the small molecules and those obtained by oxidation of LDL. 1-Fe eliminated the oxidation of DMSO to malonaldehyde completely and 1-Mn did it only partially (65% inhibition), which is consistent with the faster decomposition of hydrogen peroxide by 1-Fe relative to 1- Mn.These investigations clearly point toward the following conclusions: a) both complexes serve very well for preventing the formation of hydroxyl radical from peroxynitrite; b) the iron complex is more efficient in avoiding the formation of metal-induced hydroxyl radical; c) the manganese complex is more efficient in inhibiting the formation of reactive nitrogen species from peroxynitrite.; (i) Oxidation of small molecules by peroxynitrite; c) Sulfolane from tetramethylene sulfoxide: Peroxynitrite (6 mM) was added to a solution of tetramethylene sulfoxide (0.038 mM) in phosphate buffer solution pH 7.4 and T= 25 0C, both in the presence and absence of 38 muM 1-Fe or 1-Mn. The sulfolane was extracted into diethyl ether after 10 min of stirring and quantified by GC analysis. The same experiment was done at pH 12.7, with a reaction time of 4 hr.
  • 10
  • [ 110-52-1 ]
  • [ 126-33-0 ]
  • [ 24308-29-0 ]
  • 11
  • [ 126-33-0 ]
  • [ 109-65-9 ]
  • [ 71053-03-7 ]
  • 12
  • [ 126-33-0 ]
  • [ 74-96-4 ]
  • [ 29325-66-4 ]
  • 13
  • [ 126-33-0 ]
  • [ 74-96-4 ]
  • [ 10178-59-3 ]
  • 14
  • [ 126-33-0 ]
  • [ 13165-72-5 ]
  • 1-Methoxy-1-oxo-tetrahydro-thiophenium; chloride [ No CAS ]
  • 15
  • [ 126-33-0 ]
  • [ 593-53-3 ]
  • tetrahydro-1-methoxythiophenium 1-oxide hexafluoroantimonate [ No CAS ]
  • 16
  • [ 126-33-0 ]
  • [ 58-27-5 ]
  • [ 2197-57-1 ]
  • [ 2397-62-8 ]
  • 17
  • [ 126-33-0 ]
  • [ 106-94-5 ]
  • [ 71053-02-6 ]
  • 19
  • [ 126-33-0 ]
  • [ 74-88-4 ]
  • [ 136004-75-6 ]
  • 22
  • [ 126-33-0 ]
  • [ 104449-89-0 ]
  • 23
  • [ 126-33-0 ]
  • [ 106-98-9 ]
  • [ 187737-37-7 ]
  • [ 74-85-1 ]
  • [ 594-11-6 ]
  • [ 287-23-0 ]
  • [ 74-86-2 ]
  • 25
  • [ 4724-56-5 ]
  • [ 126-33-0 ]
  • [ 24308-29-0 ]
  • 26
  • [ 110-01-0 ]
  • [ 1600-44-8 ]
  • [ 126-33-0 ]
YieldReaction ConditionsOperation in experiment
66%; 60% With dihydrogen peroxide; In water; at 30 - 35℃; for 24h;Sealed tube; Green chemistry; General procedure: A mixture of sulfide (1 mmol) and H2O (2 mL) wastaken in a stoppered tube. Then 1.2/2.5equiv. of 50%H2O2 was added slowly to it. The reaction mixture wasstirred at room temperature. The progress of the reactionwas monitored by TLC or GC. After 24 h, the productwas extracted with ethyl acetate (3 x5 mL). The organiclayer was separated, dried (Na2SO4), and concentratedunder vacuum. The crude products were purified bycolumn chromatography using silica gel (60-120 mesh)with petroleum ether and ethyl acetate as solvent to getthe pure product. The pure products were analyzed by13C, 1H NMR spectra and gas chromatography massspectrometer (GCMS).
  • 27
  • [ 126-33-0 ]
  • [ 19300-54-0 ]
  • [ 135327-98-9 ]
YieldReaction ConditionsOperation in experiment
Sulfolane obtained in this manner was reused as solvent to separate HCl and/or HF from COF2.
  • 33
  • [ 110-01-0 ]
  • ozone containing oxygen [ No CAS ]
  • [ 126-33-0 ]
  • 35
  • [ 126-33-0 ]
  • [ 501-53-1 ]
  • [ 327618-07-5 ]
  • 36
  • [ 110-01-0 ]
  • [ 1600-44-8 ]
  • [ 126-33-0 ]
  • [ 102244-56-4 ]
  • 37
  • [ 126-33-0 ]
  • [ 4231-62-3 ]
  • [ 24463-84-1 ]
  • 38
  • [ 126-33-0 ]
  • [ 301164-69-2 ]
  • 2-(2-thienylcarbonyl)tetrahydrothiophene-1,1-dione [ No CAS ]
  • 39
  • [ 126-33-0 ]
  • [ 59046-28-5 ]
  • 2-(4-methylbenzoyl)tetrahydrothiophene-1,1-dione [ No CAS ]
  • 40
  • [ 126-33-0 ]
  • [ 375-72-4 ]
YieldReaction ConditionsOperation in experiment
With hydrogen fluoride; at -20 - 7℃;Electrolysis; Large scale; First, an electrolytic cell equipped with a reflux condenser was prepared. The capacity of the electrolytic cell is 90 dm 3, and a nickel electrode having an area of 378 dm 2 is provided as an anode and a cathode in the electrolytic cell. Subsequently, 82.6 kg (4130 mol) of anhydrous hydrogen fluoride and 9.2 kg (76.7 mol) of tetrahydrothiophene-1,1-dioxide were charged into the electrolytic bath as an electrolytic solution, respectively, and the electrolytic solution was cooled The liquid temperature of the electrolytic solution was kept at 7 C. ± 1 C. by circulating it to the vessel.Next, the reflux condenser was set at -20 C., and fluorination was carried out by electrolysis at a constant current of 800 A, 5.9 to 6.2 V. During the fluorination by the electrolytic method,The electrolytic solution was replenished by continuously supplying tetrahydrothiophene-1,1-dioxide at 0.17 kg / h and anhydrous hydrogen fluoride at 1.1 kg / h into the electrolytic cell.A product gas containing nonafluorobutanesulfonyl fluoride, hydrogen, or the like produced by an electrolytic method.
  • 41
  • [ 866251-54-9 ]
  • [ 126-33-0 ]
  • 2-(1-benzofuran-2-ylsulfonyl)tetrahydrothiophene-1,1-dioxide [ No CAS ]
  • 42
  • [ 126-33-0 ]
  • [ 1028-19-9 ]
  • 2-(toluene-4-sulfonyl)tetrahydrothiophene-1,1-dione [ No CAS ]
  • 43
  • (R)-4-methyl-benzenesulfinic acid (2,2-dimethyl-propylidene)-amide [ No CAS ]
  • [ 126-33-0 ]
  • (1R,2S,4R)-4-methyl-benzenesulfinic acid [1-(1,1-dioxo-tetrahydro-1λ6-thiophen-2-yl)-2,2-dimethyl-propyl]-amide [ No CAS ]
  • 44
  • [ 126-33-0 ]
  • [ 158009-36-0 ]
  • (1S,2S,4S)-4-methyl-benzenesulfinic acid [1-(1,1-dioxo-tetrahydro-1λ6-thiophen-2-yl)-2-methyl-propyl]-amide [ No CAS ]
  • (1S,2R,4S)-4-methyl-benzenesulfinic acid [1-(1,1-dioxo-tetrahydro-1λ6-thiophen-2-yl)-2-methyl-propyl]-amide [ No CAS ]
  • 45
  • [ 126-33-0 ]
  • [ 193979-96-3 ]
  • (1S,2S,4S)-4-methyl-benzenesulfinic acid [1-(1,1-dioxo-tetrahydro-1λ6-thiophen-2-yl)-propyl]-amide [ No CAS ]
  • (1S,2R,4S)-4-methyl-benzenesulfinic acid [1-(1,1-dioxo-tetrahydro-1λ6-thiophen-2-yl)-propyl]-amide [ No CAS ]
  • 46
  • [ 126-33-0 ]
  • [ 869277-74-7 ]
  • [ 132898-96-5 ]
YieldReaction ConditionsOperation in experiment
60.5% With trichlorophosphate; In water; ethyl acetate; 1a) 5-Chlorosulfonylisatin To a mixture of isatinsulfonic acid, sodium salt dihydrate (10 g, 35.1 mmol) and 50 mL tetramethylene sulfone was added phosphorus oxychloride (16.5 mL, 177 mmol). The resulting mixture was heated at 60 C. for 3 hours. The mixture was cooled to 0 C. and 120 mL of water was cautiously added. The resulting green solid was filtered and washed with water. The solid was dissolved in 100 mL EtOAc and washed thrice with 50 mL of water. The organic layer was dried over MgSO4, filtered and concentrated under reduced pressure to give a yellow solid. The solid was recrystallized from EtOAc/Hexanes to give the title compound as an orange solid (5.2 g, 60.5%). ES (-) MS m/e=344 (M-H).
  • 47
  • [ 126-33-0 ]
  • 2,3-dichloro-4-dimethyl-thiocarbamoyloxybenzeneacetic acid,methyl ester [ No CAS ]
  • methyl 2,3-dichloro-4-dimethylcarbamoylthiophenylacetate [ No CAS ]
YieldReaction ConditionsOperation in experiment
EXAMPLE 54 STR61 Step A: Preparation of methyl 2,3-dichloro-4-dimethylcarbamoylthiophenylacetate A solution of methyl 2,3-dichloro-4-dimethylthiocarbamoyloxyphenylacetate (5.0 g) andin tetramethylene sulfone (65 mL) was heated to reflux for 20 minutes. After 20 minutes, the reaction was cooled as rapidly as possible with a stream of air. The mixture was partitioned between water and ether. The combined organics were washed with water and brine, dried over magnessium sulfate, poured onto a column of silica gel and eluted with ethyl acetate/hexane (20/80) to give the title compound. 1 H NMR(400 MHz, CDCl3): delta 7.49 (d, 1H, J=8.3 Hz), 7.20 (d, 1H, J=8.2 Hz), 3.81 (s, 2H), 3.69 (s, 3H), 3.12 (broad s, 3H), 3.00 (broad s, 3H).
  • 48
  • [ 126-33-0 ]
  • [ 143945-53-3 ]
  • [ 155399-60-3 ]
YieldReaction ConditionsOperation in experiment
With n-butyllithium; ammonium chloride; In tetrahydrofuran; EXAMPLE 12 2-Butyl-6-[hydroxy(tetrahydro-2-thienyl)methyl]-4(1H)-quinazolinone S,S-dioxide A solution of 2 ml of tetramethylenesulfone in 20 ml of dry tetrahydrofuran is cooled to 0 C. and 6.4 ml of n-butyl lithium is added dropwise. After stirring at 0 C. for 30 minutes the mixture is cooled to -78 C. and 0.920 g of 2-butyl-1,4-dihydro-4-oxo-6-quinazolinecarboxaldehyde added in small portions. The reaction mixture is stirred at -78 C. for 4.5 hours and then allowed to warm to 0 C. The reaction mixture is quenched with 20 ml of saturated ammonium chloride and stirred for 30 minutes. The reaction mixture is concentrated under vacuum and extracted with three 50 ml portions of ethyl acetate. The combined extracts are dried with anhydrous sodium sulfate and evaporated to a residue which is heated with 1:1 ethyl acetate-hexanes to afford 0.580 g of solid upon cooling. The solid is purified by chromatography on silica gel using 3:1 ethyl acetate-hexanes to give 0.360 g of the desired product, m.p. 207-209 C.
  • 49
  • [ 126-33-0 ]
  • [ 7651-83-4 ]
  • [ 56623-93-9 ]
YieldReaction ConditionsOperation in experiment
100% With nitronium tetrafluoroborate; In methanol; IV. Synthesis of 7-Hydroxy-8-nitroisoquinoline To a 300 ml round bottom flask is added 14.5 g (0.1 mole) of 7-hydroxyisoquinoline and 100 ml of warmed tetramethylene sulfone. The brown slurry is stirred and to it is added portionwise 18.6 g (0.14 mole) of nitronium tetrafluoroborate with cooling (ice bath). The reaction is stirred for 3 hours. The reaction is then quenched with 100 ml of methanol, evaporated to dryness and triturated twice with ether to precipitate a dark solid (19.0 g, 100%).
100% With nitronium tetrafluoroborate; In methanol; IV. Synthesis of 7-Hydroxy-8-nitroisoquinoline To a 300 ml round bottom flask is added 14.5 g (0.1 mole) of 7-hydroxyisoquinoline and 100 ml of warmed tetramethylene sulfone. The brown slurry is stirred and to it is added portionwise 18.6 g (0.14 mole) of nitronium tetrafluoroborate with cooling (ice bath). The reaction is stirred for 3 hours. The reaction is then quenched with 100 ml of methanol, evaporated to dryness and triturated twice with ether to precipitate a dark solid (19.0 g, 100%).
  • 50
  • [ 126-33-0 ]
  • [ 7355-58-0 ]
  • [ 1120-64-5 ]
YieldReaction ConditionsOperation in experiment
73% EXAMPLE 1 Preparation of 2-methyl-1,3-oxazoline was as follows. To 10 milliliters (ml) of tetramethylene sulfone (<strong>[126-33-0]Sulfolane</strong>) was added N-(2-chloroethyl) acetamide (2 grams (g), 16 millimoles (mmole)) and 4 equivalents (10 g) of 40% potassium fluoride on alumina. This mixture was mechanically stirred for about two hours. The product was then distilled at 90 C under a vacuum of 550 mm Hg to give 1.018 g (a yield of about 73 percent).
  • 51
  • [ 126-33-0 ]
  • [ 115812-33-4 ]
  • 2H-tetrachlorobenzotrifluoride [ No CAS ]
  • [ 2751-90-8 ]
  • 2H-tetrafluorobenzotrifluoride [ No CAS ]
YieldReaction ConditionsOperation in experiment
90.5% With potassium fluoride; d) 812 g (14 mol) of potassium fluoride and 1400 ml of tetramethylene sulphone are subjected to incipient distillation at 20 mbar (quantity of distillate: 100 ml) in a stirred V4A steel apparatus. Then 40 g of tetraphenylphosphonium bromide and a mixture of 795 g (2.8 mm) of 2H-tetrachlorobenzotrifluoride and 170 g (0.78 mm) of 5-chloro-2,3,4-trifluorobenzotrifluoride are added and the mixture is stirred for 18 hours at 210 C. under the autogenous pressure (max. pressure 3.4 bar). Distillation yields 747 g of a crude distillate which is redistilled in a rotating strip column. 396 g of 2H-tetrafluorobenzotrifluoride and 318 g of 5-chloro-2,3,4-trifluorobenzotrifluoride are obtained. The recovery rate of the isolated yield is 90.5%.
  • 52
  • [ 126-33-0 ]
  • [ 18611-43-3 ]
  • [ 99728-16-2 ]
YieldReaction ConditionsOperation in experiment
In HF; Preparation of 1-chloro-3,3,3-trifluoropropene from 1,1,3,3-tetrachloropropene A 450 ml hastelloy autoclave, fitted with a condenser and pressure regulator, was evacuated and cooled in a dry ice/acetone bath. The condenser was maintained at 0 C. The reactor was charged with 75 ml tetramethylene sulfone (<strong>[126-33-0]Sulfolane</strong>). The reactor was then cooled in a dry ice/acetone bath and charged with 134 g (6.7 mole) of HF and 180 g (1.0 mole) of 1,1,3,3-tetrachloropropene. The reactor was heated to 100 C. and the pressure maintained at 230 p.s.i. by venting HCl through the back pressure regulator. When HCl evolution ceased, the reactor was cooled to 70 C. and discharged through a KOH scrubber and into a separatory funnel full of ice. The product was decanted as the more dense layer into a chilled bottle. An average isolated yield of 115 g (86%) was achieved for each of 4 consecutive runs. After washing, 2.3 g of oligomeric material was recovered from the reactor in each run.
  • 53
  • [ 126-33-0 ]
  • [ 61841-45-0 ]
  • [ 393-01-1 ]
  • [ 120770-03-8 ]
YieldReaction ConditionsOperation in experiment
With potassium fluoride; 3-Chloro-2,4-difluoro-benzotrifluoride 3,700 g of potassium fluoride are initially introduced into 10,000 ml of tetramethylene sulphone in a stirred apparatus with exclusion of moisture, and 500 ml of tetramethylene sulphone are distilled off under a pressure of 16 mbar. 3,965 g of 2,3,4-trichlorobenzotrifluoride are then metered in and the mixture is heated to 230 C. The product formed is taken off via a column with a reflux divider. After three hours, a slight vacuum is applied and the mixture is subjected to incipient distillation up to the boiling point of tetramethylene sulphone. The coarse distillate (3,390 g) is subjected to fine distillation. The first runnings of 396 g comprise mainly 2,3,4-trifluoro-benzotrifluoride (boiling point 92-142 C.; the main runnings (3,051 g) have a boiling point of 142-143 C. and comprise 3-chloro-2,4-difluorobenzotrifluoride to the extent of 97.6%.
  • 54
  • [ 126-33-0 ]
  • [ 61841-45-0 ]
  • [ 120770-03-8 ]
YieldReaction ConditionsOperation in experiment
With potassium fluoride; 3-Chloro-2,4-difluoro-benzotrifluoride 800 g of potassium fluoride and 2500 ml of tetramethylene sulphone are initially introduced into a stirred apparatus and the mixture is subjected to incipient distillation under a pressure of 15 mbar until about 200 ml of solvent have passed over. 1100 g of 2,3,4-trichlorobenzotrifluoride are then metered in at a temperature of 150 C. and the mixture is heated to 220 C. with exclusion of moisture. The product is taken off over a column with a reflux divider; the mixture is kept at this temperature for a total of 12 hours. The content of fluoroaromatics is then distilled off under reduced pressure. After redistillation of the reaciton mixture, 652 g of 3-chloro-2,4-difluoro-benzotrifluoride are obtained, after first runnings comprising 2,3,4-trifluoro-benzotrifluoride, in a boiling range of 37-40 C./16 mbar.
  • 55
  • [ 126-33-0 ]
  • [ 91-14-5 ]
  • [ 107-21-1 ]
  • [ 21792-52-9 ]
YieldReaction ConditionsOperation in experiment
With potassium hydroxide; hydrogen bromide; bromine; In water; EXAMPLE 2 In Example 2, diethynylbenzene was prepared from divinylbenzene using potassium hydroxide in place of sodium hydroxide. A three-necked, five-liter, round-bottom flask, equipped with an air-driven teflon paddle stirrer, a 250 ml vapor-bypass dropping funnel and a Y adapter provided with a pot thermometer, a gas inlet side arm and a condenser was charged with 700 ml of tetramethylene sulfone (about 880 grams) (Aldrich, 99%) and 274 grams (2.11 mole) of divinylbenzene (Dow Chemical Co.). The mixture was stirred and cooled to 20 C. with an ice water bath. Liquid bromine was added dropwise over 11/2 hours so as to maintain the temperature at 20-28 C. with no loss of Br2 vapor from the system. A total of 634 gms. (3.96 moles) of bromine was added, and the dark reaction mixture was allowed to stand overnight. The mixture was stirred an additional two hours at room temperature, then 41.6 grams of polyethylene glycol (PEG-400; Aldrich) was added, (about 2% of the mixture by weight) and the stirred mixture was cooled to 1720 -18 C. To this was then added dropwise a 60% KOH solution (1375 grams of KOH pellets (85% KOH) in 916 grams distilled water, 20.9 moles KOH, 2290 grams of solution amounting to a 160 mole % excess) over about one hour while maintaining the temperature in the 18-27 C. range with ice-bath cooling. The reaction exotherm is confined to the reaction of the first half of the KOH addition, which coincides with the removal of the first two moles of HBr. The removal of the second two moles of HBr leading to the acetylenic formation is endothermic. The reaction mixture was then heated to 80 C. for two hours. The system was rearranged for steam distillation, and the reaction mixture was then steam distilled at about 110 C. for about 11/2 hours to yield about two liters of distillate. The top layer of diethynylbenzene was separated (146.7 grams) and was dried over Na2 SO4 in a dark bottle. The remainder of the steam distillate (aqueous layer) was extracted with 250 ml of ether and dried over Na2 SO4. When evaporated, 2.1 grams of product was yielded. Steam distillation was continued to yield another liter of steam distillate which was extracted with 250-350 ml of ether. The dried ether extract (Na2 SO4) was evaporated to yield 11 grams of product. The solution in the flask, upon standing overnight at ambient temperature, separated into two layers. The bottom aqueous layer was separated and discarded; the remainder was steam distilled to afford two more distillates of about one liter each. The first of these was extracted with 300 Ml of ether and after drying over Na2 SO4, yielded 18.93 grams of oily product. The pot residue was discarded. The total of product fractions totalled 182.6 grams, corresponding to a yield of 68.7%. An analysis of the principal fraction by gas liquid chromatography produced the following results:
 

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