Home Cart 0 Sign in  

[ CAS No. 251-41-2 ]

{[proInfo.proName]} ,{[proInfo.pro_purity]}
Cat. No.: {[proInfo.prAm]}
Chemical Structure| 251-41-2
Chemical Structure| 251-41-2
Structure of 251-41-2 * Storage: {[proInfo.prStorage]}

Quality Control of [ 251-41-2 ]

Related Doc. of [ 251-41-2 ]

SDS
Alternatived Products of [ 251-41-2 ]
Alternatived Products of [ 251-41-2 ]

Product Details of [ 251-41-2 ]

CAS No. :251-41-2 MDL No. :MFCD00179479
Formula : C6H4S2 Boiling Point : -
Linear Structure Formula :- InChI Key :N/A
M.W :140.23 g/mol Pubchem ID :136063
Synonyms :

Safety of [ 251-41-2 ]

Signal Word:Warning Class:N/A
Precautionary Statements:P261-P305+P351+P338 UN#:N/A
Hazard Statements:H302-H315-H319-H335 Packing Group:N/A
GHS Pictogram:

Application In Synthesis of [ 251-41-2 ]

  • Upstream synthesis route of [ 251-41-2 ]
  • Downstream synthetic route of [ 251-41-2 ]

[ 251-41-2 ] Synthesis Path-Upstream   1~15

  • 1
  • [ 52-90-4 ]
  • [ 50-81-7 ]
  • [ 1940-01-8 ]
  • [ 1468-83-3 ]
  • [ 24295-03-2 ]
  • [ 251-41-2 ]
  • [ 23654-92-4 ]
  • [ 867253-51-8 ]
Reference: [1] Food Chemistry, 2010, vol. 121, # 4, p. 1060 - 1065
  • 2
  • [ 52-90-4 ]
  • [ 50-81-7 ]
  • [ 1940-01-8 ]
  • [ 1468-83-3 ]
  • [ 24295-03-2 ]
  • [ 251-41-2 ]
  • [ 23654-92-4 ]
  • [ 867253-51-8 ]
Reference: [1] Food Chemistry, 2010, vol. 121, # 4, p. 1060 - 1065
  • 3
  • [ 52-90-4 ]
  • [ 50-81-7 ]
  • [ 1940-01-8 ]
  • [ 24295-03-2 ]
  • [ 251-41-2 ]
  • [ 13393-75-4 ]
  • [ 23654-92-4 ]
  • [ 867253-51-8 ]
Reference: [1] Food Chemistry, 2010, vol. 121, # 4, p. 1060 - 1065
  • 4
  • [ 52-90-4 ]
  • [ 50-81-7 ]
  • [ 1940-01-8 ]
  • [ 24295-03-2 ]
  • [ 251-41-2 ]
  • [ 13393-75-4 ]
Reference: [1] Food Chemistry, 2010, vol. 121, # 4, p. 1060 - 1065
  • 5
  • [ 52-90-4 ]
  • [ 50-81-7 ]
  • [ 1940-01-8 ]
  • [ 24295-03-2 ]
  • [ 251-41-2 ]
  • [ 13393-75-4 ]
  • [ 151602-63-0 ]
  • [ 867253-51-8 ]
Reference: [1] Food Chemistry, 2010, vol. 121, # 4, p. 1060 - 1065
  • 6
  • [ 52-90-4 ]
  • [ 50-81-7 ]
  • [ 1940-01-8 ]
  • [ 24295-03-2 ]
  • [ 251-41-2 ]
  • [ 867253-51-8 ]
Reference: [1] Food Chemistry, 2010, vol. 121, # 4, p. 1060 - 1065
  • 7
  • [ 251-41-2 ]
  • [ 1723-27-9 ]
Reference: [1] Journal of the Chemical Society, 1940, p. 305,308
[2] Journal of Medicinal Chemistry, 2017, vol. 60, # 7, p. 2697 - 2717
  • 8
  • [ 251-41-2 ]
  • [ 25121-87-3 ]
YieldReaction ConditionsOperation in experiment
99% With N-Bromosuccinimide In N,N-dimethyl-formamide at 20℃; Thienothiophene(2.01 g of Tokyo Chemical Industry Co., Ltd.) and 30 mL of dimethylformamide (DMF) were placed in a reaction vessel.After stirring at room temperature to confirm dissolution,6.10 g (2.4 eq) of N-bromosuccinimide (NBS) was put in a powder state.After confirming the disappearance of the raw materials, n-hexane and ion-exchanged water were added to the reaction solution.Perform liquid separation.After washing the organic layer with ion-exchanged water and saturated saline once,Drying was carried out using Na2SO4.Distilling off the solvent under reduced pressure and dryingThiophenethiophene dibromide4.21g (99percent yield).
95% With N-Bromosuccinimide In N,N-dimethyl-formamide at 0℃; for 12 h; Added to the reactor 30 mlDMF, thieno [3, 2 - b] thiophene (2.31 g, 16.5 mmol), followed by cooling to 0 °C, adding NBS (8.81 g, 49.5 mmol), light reaction 12 h, NaHSO reaction after the conclusion3Washing, removing the upper layer solvent, congeals the organic phase concentration, over silica gel column purification to obtain compound C - 21 - 1 (4.67 g, 95percent).
88% With N-Bromosuccinimide In DMF (N,N-dimethyl-formamide) at 20℃; for 3 h; N-bromosuccinimide (1.24 g, 6.94 mmol) was added to a solution of thieno [3,2-b]thiophene (1.0 g, 6.94 mmol) in DMF (30 ml) at room temperature and this mixture was stirred for 3h. After this water ( 100 ml) was added and the precipitate formed was filtrated off, washed with water and dried to give 2 as a white solid (1.87 g, 88 percent). 1H NMR (300 MHz, CDCl3): 8 (ppm) 7.14 (s, 2H, Ar-H); 13C NMR (75 MHz, CDC13): 8 (ppm) 138.3 (quat.), 121.8 (CH), 113.7 (quat.)
85% at 20℃; Inert atmosphere A solution of 1.55 g (8.7 mmol) of N-bromosuccinimide (NBS) in 1 ml of DMF was slowly added in a stirred solution of 0.61 g (4.35 mmol) of thieno[3,2-b]thiophene in 9 ml of DMF. The reaction mixture was stirred overnight. The product was extracted with dichloromethane and the organic phase was washed 3 times with water, dried with MgSO4 and the organic solvent was removed with roto-evaporation. The resulting crude residue was purified by column chromatography on silica gel with hexane/dichloromethane 9/1 to give a white solid (1 g, 85percent yield). (m.p. 116.4-118.6 °C) δH (200 MHz, CDCl3) 7.19 (1H, s, 1-H), δC (50 MHz, CDCl3) 128.6, 122.2, 114.4.
68% With N-Bromosuccinimide In tetrahydrofuran at 10℃; for 80 h; Inert atmosphere 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, 68percent yield). 1H NMR (300 MHz, CDCl3):δ (ppm) 7.14 (s, 2H). 13C NMR (75 MHz, CDCl3):δ (ppm) 138.31, 121.75, 113.64. GC-MS (EI, m/z) calcd for (C6H2Br2S2):297.79, found: 297.77.

Reference: [1] Patent: TWI630193, 2018, B, . Location in patent: Paragraph 0104; 0105
[2] Chemistry - A European Journal, 2011, vol. 17, # 3, p. 866 - 872
[3] Angewandte Chemie - International Edition, 2013, vol. 52, # 10, p. 2920 - 2924[4] Angew. Chem., 2013, vol. 125, # 10, p. 2992 - 2996,5
[5] Tetrahedron Letters, 2009, vol. 50, # 51, p. 7148 - 7151
[6] Patent: CN107056798, 2017, A, . Location in patent: Paragraph 0061; 0062; 0063; 0064
[7] Journal of Nanoscience and Nanotechnology, 2010, vol. 10, # 10, p. 6800 - 6804
[8] Journal of Organic Chemistry, 2015, vol. 80, # 20, p. 10127 - 10133
[9] Macromolecules, 2013, vol. 46, # 3, p. 727 - 735
[10] Patent: WO2005/121150, 2005, A1, . Location in patent: Page/Page column 33
[11] Organic Electronics: physics, materials, applications, 2014, vol. 15, # 4, p. 943 - 953
[12] Dyes and Pigments, 2015, vol. 116, p. 146 - 154
[13] Polymer, 2012, vol. 53, # 12, p. 2334 - 2346
[14] Journal of the Institute of Petroleum, 1948, vol. 34, p. 226,229
[15] Dalton Transactions, 2005, # 5, p. 874 - 883
[16] Molecules, 2012, vol. 17, # 10, p. 12163 - 12171
[17] Journal of the American Chemical Society, 2013, vol. 135, # 6, p. 2040 - 2043
[18] Patent: US8779204, 2014, B2, . Location in patent: Page/Page column 13; 14
[19] Patent: KR101540066, 2015, B1, . Location in patent: Paragraph 0021; 0022; 0023
  • 9
  • [ 251-41-2 ]
  • [ 124638-53-5 ]
YieldReaction ConditionsOperation in experiment
95% With bromine; acetic acid In chloroform at 20 - 78℃; S1,willAnd thiophenethienothiophene(5 g, 35.7 mmol)Soluble in glacial acetic acid (36ml)And chloroform (10 ml)Of the mixed solvent,Br2 is added dropwise at room temperature(28.5 g, 180.56 mmol),Continue to stir for half an hour,And then heated to reflux at room temperature of 78 ° C overnight; Ling to room temperature, washed with water, precipitation of white solid compounds, and then washed with water and methanol 3 times, vacuum drying at room temperature,To give white solid compound 1, [M +] = 455.0 (yield: 95percent);
93%
Stage #1: With acetic acid In chloroform for 1 h; Inert atmosphere
Stage #2: With bromine In chloroform for 1 h; Reflux
In the reactor into the thieno [3, 2 - b] thiophene (4.21 g, 30 mmol), under the protection of nitrogen, acetic acid is added into the reactor 30 ml, chloroform 50 ml, will be 20 mmol of Br2Solution is dripped slowly into the reaction in the reactor, stirring after 1 h, then gradually adding 15 mmol of Br2, Stirring 1 h, reflux overnight, cooled to the room temperature, to obtain the solid precipitation, successively de-ionized water and methanol washing, drying, the obtained crude product over silica gel column, to obtain compound C - 1 - 1 (12.72 g, 93percent).
91% With bromine In chloroform at 60℃; for 24 h; Inert atmosphere In an inert atmosphere, the bromine (9.2 ml; 28.5 g; 178.2 mmoles) diluted in 40 ml of chloroform is added to a solution of thienothiophene (5g; 35.7 mmoles) in 40 ml of chloroform, by slow dripping. The temperature is brought to 60°C. After 24 hours, it is brought to 20°C and a 1 M aqueous solution of sodium thiosulfate is added until the excess bromine is completely destroyed. The precipitate is filtered and washed first with water and then with chloroform. 14.6 g of 2,3,5,6-tetrabromothieno[3,2-b]thiophene of formula (VI) are obtained with a 91 percent yield:
Reference: [1] Patent: CN106188090, 2016, A, . Location in patent: Paragraph 0086
[2] Patent: CN107056798, 2017, A, . Location in patent: Paragraph 0055; 0056; 0057
[3] Patent: WO2016/92065, 2016, A1, . Location in patent: Page/Page column 21
[4] Journal of Materials Chemistry C, 2018, vol. 6, # 16, p. 4471 - 4478
[5] Bulletin of the Chemical Society of Japan, 1989, vol. 62, # 5, p. 1547 - 1555
[6] J. Inst. Petr. Technol., 1935, vol. 21, p. 135,148
[7] Chemical Communications, 2005, # 9, p. 1161 - 1163
[8] Patent: US2009/43113, 2009, A1, . Location in patent: Page/Page column 6
[9] Chemistry - An Asian Journal, 2010, vol. 5, # 7, p. 1550 - 1554
[10] New Journal of Chemistry, 2013, vol. 37, # 4, p. 1189 - 1194
[11] Chemical Communications, 2015, vol. 51, # 60, p. 11961 - 11963
  • 10
  • [ 251-41-2 ]
  • [ 68-12-2 ]
  • [ 31486-86-9 ]
YieldReaction ConditionsOperation in experiment
75% With trichlorophosphate In 1,2-dichloro-ethane at 0 - 20℃; Thieno[3,2-b]thiophene (3.00g, 21.4mmol) was taken in a 100mL round bottom flask in ethylene dichloride (75.0mL) and dimethylformamide (1.65mL, 21.4mmol) was added at room temperature. The resulting reaction solution was cooled to 0°C and POCl3 (5.87mL, 64.3mmol) was added drop-wise. The reaction mixture was allowed to warm to room temperature and heated at reflux overnight. The reaction mixture was treated with a saturated solution of sodium acetate and the organic layer was separated. The organic layer was washed with water followed by brine, dried over anhydrous sodium sulphate and the solvent was evaporated in vacuo to give a crude dark yellow oil, which was purified by column chromatography on silica (hexane:ethyl acetate 9:1) to give the title compoundS1 (2.70g, 75percent) as a light yellow oil. Rf (10percent ethyl acetate/hexane) 0.45; 1H NMR (400MHz, CD3COCD3, 25°C, ppm) δ 10.05 (s, 1H), 8.33 (s, 1H), 8.00–7.99 (m, 1H), 7.57–7.55 (m, 1H); 13C NMR (100.6MHz, CDCl3, 25°C, ppm) δ 183.7, 145.9, 145.6, 139.4, 134.1, 129.3, 120.3; HRMS (APCI): calcd for C7H5OS2 (M+H)+ 168.9775; found 168.9776.
74.98% With trichlorophosphate In 1,2-dichloro-ethane at 0℃; Reflux Compound Example 4.; Step 1 . Synthesis of thieno[3,2-blthiophene-2-carbaldehyde; Thieno[3,2-b]thiophene (3 g, 21.43 mmol) was taken in ethylene dichloride (75 ml) in a 250 ml round bottom flask followed by the addition of dimethylformamide (1.65 ml, 21 .43 mmol) at RT. The resulting reaction solution was cooled to 0°C and POCI3 (5.87 ml, 64.29 mmol) was added to it. The reaction mixture was allowed to warm to RT and refluxed for overnight. Reaction mix was allowed to cool down, worked up with saturated sodium acetate solution and product was extracted in ethyl acetate. The organic layer was washed twice with water followed by brine and dried over Na2S04 and recovered to afford crude yellow oil which was subjected to column chromatography on silica (Hexane:Ethyl acetate (9:1 )) to afford 2.7 g (74.98percent) of thieno[3,2-b]thiophene-2-carbaldehyde as light yellow oil.1H NMR (200MHz, DMSO) δ 9.97 (s, IH), 8.39 (m, 1 H), 8.07 (m, 1 H), 7.55 (m, 1 H)
67% With trichlorophosphate In 1,2-dichloro-ethane at 0 - 80℃; for 5 h; Inert atmosphere In a 250 mL 3-necked flask, asolution of DMF (21.9 g, 300 mmol) in dry 1,2-dichloroethane (50 mL) was cooled to 0 °C under a nitrogen atmosphere. Following this, POCl3 (23.0 g, 150mmol) was added dropwise with stirring. When all the POCl3 had been added, and the heat of the reaction had subsided, a solution of thienothiophene (TT) (14.0 g, 100 mmol) in 1,2-dichloroethane (50 mL) was added dropwise. The reaction mixture was stirred for 5 h at 80 °C and then poured into cold saturated solution of sodium bicarbonate (200 mL) and extracted with DCM. The organic layer was washed with water and dried over anhydrous MgSO4. After removing the solvent, the crude product obtained was purified by column chromatography (PE/EA = 15/1, v/v) to give a light yellow solid (11.3 g, 67percentyield). 1H NMR (300 MHz, CDCl3): δ (ppm) 9.96 (s, 1H),7.93 (s, 1H), 7.69 (d, J = 5.1 Hz, 1H), 7.33 (d, J = 5.4 Hz, 1H).13C NMR (75 MHz, CDCl3): δ (ppm) 183.54, 145.73, 145.47,139.23, 133.90, 129.06, 120.16. GC-MS (EI,m/z) calcd. for (C7H4OS2): 167.97. Found:168.03.
Reference: [1] Journal of Materials Chemistry C, 2015, vol. 3, # 2, p. 370 - 381
[2] Chemistry - A European Journal, 2014, vol. 20, # 34, p. 10685 - 10694
[3] Dyes and Pigments, 2015, vol. 119, p. 122 - 132
[4] Patent: WO2011/137487, 2011, A1, . Location in patent: Page/Page column 31
[5] Dyes and Pigments, 2015, vol. 120, p. 85 - 92
[6] Journal of Materials Chemistry A, 2016, vol. 4, # 22, p. 8784 - 8792
[7] Journal of Medicinal Chemistry, 2017, vol. 60, # 7, p. 2697 - 2717
[8] Journal of Organic Chemistry, 2008, vol. 73, # 12, p. 4608 - 4614
[9] Patent: US6642237, 2003, B1, . Location in patent: Page/Page column 125-126
[10] Journal of Materials Chemistry A, 2013, vol. 1, # 37, p. 11295 - 11305
[11] RSC Advances, 2013, vol. 3, # 44, p. 22544 - 22553
  • 11
  • [ 251-41-2 ]
  • [ 93-61-8 ]
  • [ 31486-86-9 ]
Reference: [1] Heteroatom Chemistry, 2013, vol. 24, # 1, p. 25 - 35
  • 12
  • [ 2591-86-8 ]
  • [ 251-41-2 ]
  • [ 31486-86-9 ]
Reference: [1] Synlett, 2011, # 15, p. 2151 - 2156
  • 13
  • [ 251-41-2 ]
  • [ 392662-65-6 ]
Reference: [1] Chemical Communications, 2005, # 9, p. 1161 - 1163
[2] Macromolecules, 2013, vol. 46, # 3, p. 727 - 735
[3] Patent: WO2016/92065, 2016, A1,
[4] Patent: CN107056798, 2017, A,
  • 14
  • [ 251-41-2 ]
  • [ 61676-62-8 ]
  • [ 924894-85-9 ]
YieldReaction ConditionsOperation in experiment
61.25%
Stage #1: With n-butyllithium In tetrahydrofuran; hexanes at -78℃; for 1.16667 h; Inert atmosphere; Cooling with ice
Stage #3: With ammonium chloride In tetrahydrofuran; hexanes; water
To a solution of thieno[3,2-b]thiophene (1 .5 g, 10.70 mmol) in THF (25.5 mL) at -78 °C under N 2 is added dropwise a solution of BuLi in hexanes (8.988 mL of 2.5 M, 22.47 mmol), stirred for 20 min, cooling bath is replaced with ice bath and stirred for 50 min. The resultant thick suspension is quenched with 2- isopropoxy-4,4,5,5-tetramethyl-1 ,3,2-dioxaborolane (4.181 g, 4.584 mL, 22.47 mmol). The reaction mixture is kept for overnight and then quenched with saturated aq. NH4Cl solution. After extraction with CH2Cl2 (2 x 100 mL), the combined extracts are washed with brine and dried (Na2S04). Organic solution is diluted with -20 mL of ethyl acetate, concentrated slowly on rotary evaporator until CH2Cl2 is removed. The resultant white fine crystals are collected by filtration. The solid is washed with heptanes and dried under high vacuum to afford 4,4,5,5-tetramethyl-2-[5-(4,4,5,5-tetramethyl-1 ,3,2- dioxaborolan-2-yl)thieno[3,2-b]thiophen-2-yl]-1 ,3,2-dioxaborolane (2.57 g, 6.554 mmol, 61.25percent) as half-white solid. 1H NMR (400 MHz, CDCl3) δ 7.75 (s, 2H), 1.343 (s, 12H).
Reference: [1] Patent: WO2011/119853, 2011, A1, . Location in patent: Page/Page column 126-127
[2] Patent: WO2011/119858, 2011, A1, . Location in patent: Page/Page column 86
  • 15
  • [ 251-41-2 ]
  • [ 25015-63-8 ]
  • [ 924894-85-9 ]
Reference: [1] Dalton Transactions, 2015, vol. 44, # 29, p. 13007 - 13016
Historical Records