6287-82-7|2,3-Dibromobenzo[b]thiophene| Ambeed

Structure of 6287-82-7

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Quality Control of [ 6287-82-7 ] Purity: 98% (stabilized with Cu+HQ+MgO) SDS Specification

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Twofold 6π‐Electrocyclization as a Route Toward Multi‐Heteroatom‐Doped Nanographenes Built on 1, 4‐Dihydropyrrolo [3, 2‐b] pyrrole Core

Górski, Krzysztof ; Pejov, Ljupcho ; Jørgensen, Kåre B ; Knysh, Iryna ; Jacquemin, Denis ; Gryko, Daniel T

DOI: 10.1002/chem.202404094 PubMed ID: 39587457 Chem. Eur. J.,2024,e202404094.

Abstract: Here we present a highly versatile synthetic strategy based on twofold 6π-electrocyclization accompanied with HBr elimination as a novel approach towards centrosymmetric multi-heteroatom-doped nanographenes build around an electron-rich 1,4-dihydropyrrolo[3,2-b]pyrrole core. A straightforward synthesis from readily available substrates offers a unique possibility of fusing the 1,4-dihydropyrrolo[3,2-b]pyrrole subunit not only with carbocyclic building blocks, such as electron-deficient phenanthrenes, chrysenes, or [4]helicenes, but also with heterocyclic systems, such asbenzo[b]furan and 5-thiatruxene. The clear advantage of this strategy is that there is no requirement to assemble complex scaffolds possessing bromoaryl units since bromine atom is introduced by bromination of 1,4-dihydropyrrolo[3,2-b]pyrrole core which, because of its exceptionally electron-rich character, is straightforward reaction. The obtained χ-shaped and S-shaped nanographenes containing 10or more fused rings, exhibit visible-range emissions characterized by fluorescence quantum yields reaching 48%. Computational studies of the reaction mechanism revealed that the 6π-electrocyclization is kinetically favourable over photo-induced direct arylation. Steadystate UV/Visible spectroscopy reveals that upon photoexcitation, the prepared S-shaped N-doped nanographenes undergo mostly radiative relaxation leading to large fluorescence quantum yields. We anticipate that this chemistry will empower the creation of new materials with various functionalities.

Keywords: Dyes/Pigments ; Photochemistry ; Nanographenes ; Pyrrole ; Fluorescence

Purchased from AmBeed: 26465-81-6 ; 113893-08-6 ; 6287-82-7 ; 128-08-5

Product Details of [ 6287-82-7 ]

CAS No. :	6287-82-7
Formula :	C₈H₄Br₂S
M.W :	291.99
SMILES Code :	BrC1=C(Br)SC2=CC=CC=C21
MDL No. :	MFCD06798119
InChI Key :	TWZSIAFEFBKCNN-UHFFFAOYSA-N
Pubchem ID :	94977

Safety of [ 6287-82-7 ]

GHS Pictogram:
Signal Word:	Warning
Hazard Statements:	H317-H319
Precautionary Statements:	P280-P305+P351+P338

Computational Chemistry of [ 6287-82-7 ] Show Less

Physicochemical Properties

Num. heavy atoms	11
Num. arom. heavy atoms	9
Fraction Csp3	0.0
Num. rotatable bonds	0
Num. H-bond acceptors	0.0
Num. H-bond donors	0.0
Molar Refractivity	57.23
TPSA ? Topological Polar Surface Area: Calculated from Ertl P. et al. 2000 J. Med. Chem.	28.24 Å²

Lipophilicity

Log P_o/w (iLOGP)? iLOGP: in-house physics-based method implemented from Daina A et al. 2014 J. Chem. Inf. Model.	2.63
Log P_o/w (XLOGP3)? XLOGP3: Atomistic and knowledge-based method calculated by XLOGP program, version 3.2.2, courtesy of CCBG, Shanghai Institute of Organic Chemistry	3.96
Log P_o/w (WLOGP)? WLOGP: Atomistic method implemented from Wildman SA and Crippen GM. 1999 J. Chem. Inf. Model.	4.43
Log P_o/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.	4.09
Log P_o/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	4.99
Consensus Log P_o/w? Consensus Log P_o/w: Average of all five predictions	4.02

Water Solubility

Log S (ESOL):? ESOL: Topological method implemented from Delaney JS. 2004 J. Chem. Inf. Model.	-4.75
Solubility	0.00519 mg/ml ; 0.0000178 mol/l
Class? Solubility class: Log S scale Insoluble < -10 < Poorly < -6 < Moderately < -4 < Soluble < -2 Very < 0 < Highly	Moderately soluble
Log S (Ali)? Ali: Topological method implemented from Ali J. et al. 2012 J. Chem. Inf. Model.	-4.25
Solubility	0.0163 mg/ml ; 0.0000558 mol/l
Class? Solubility class: Log S scale Insoluble < -10 < Poorly < -6 < Moderately < -4 < Soluble < -2 Very < 0 < Highly	Moderately 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	-5.04
Solubility	0.00267 mg/ml ; 0.00000914 mol/l
Class? Solubility class: Log S scale Insoluble < -10 < Poorly < -6 < Moderately < -4 < Soluble < -2 Very < 0 < Highly	Moderately 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	Yes
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	Yes
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	Yes
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.	-5.27 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)	2.59

Application In Synthesis of [ 6287-82-7 ]

* 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 [ 6287-82-7 ]

[ 6287-82-7 ] Synthesis Path-Downstream 1~41

1
[ 95-15-8 ]
[ 6287-82-7 ]

Yield	Reaction Conditions	Operation in experiment
100%	With bromine; potassium acetate; In dichloromethane;	In the DCM solvent, in the presence of potassium acetate, benzothiophene (11) was brominated using bromine the benzothiophene. A white solid of compound (12) was obtained in a yield of 100%. In addition, equation (1) when manufacturing the compound shown, compound (11) gives the desired compound X can be replaced.
99%	With bromine; In chloroform; at 20℃; for 19.5h;	A solution of 18 g (134 mmol) of benzo[b]thiophene in 200 mL of chloroform was stirred and to this mixture was added 42.9 g (13.7 mL, 268 mmol) of bromine in 100 mL of chloroform dropwise at RT over 1.5 h. After stirring for 18 h, solid NaHCO3 was added to neutralize the hydrobromic acid. The organic layer was washed with water and Na2S2O8 and dried (MgSO4). On evaporation of the solvent solid was obtained which was crystallized from methanol to give 38.8 g (99%) of 2,3-dibromobenzo[b]thiophene.
90%	With bromine; In chloroform; at 0℃; for 12h;	Benzo[b]thiophene (10 g, 74.5 mmol) was dissolved in 250 ml of chloroform. The resulting solution was cooled down to 0C and bromine (7.87 ml, 152.8 mmol) was added. The mixture was stirred for 12h. The reaction mixture was poured into water and extracted with chloroform. The organic layer was separated, dried over anhydrous magnesium sulfate, and evaporated under reduced pressure to afford (3) as a white solid, yield 90%. 1H NMR (CDCl3, 400MHz) 7.76-7.74 (d, J=8.8Hz, 1H), 7.73-7.71 (d, J=8Hz, 1H), 7.45-7.41 (t, J=7.6Hz, 1H), 7.41-7.36 (t, J=8Hz, 1H) ppm.

84%	With bromine; potassium acetate; In dichloromethane; at 20℃;Reflux;	To a CH2Cl2 solution (50 mL) of benzo[b]thiophene (14, 5.00 g, 37.3 mmol) and KOAc (7.30 g, 74.6 mmol) was added Br2 (3.8 mL, 74.6 mmol) at 20 C, and the solution was heated under reflux for 24 h. To the solution was added a satd solution of Na2S2O3 and NaHCO3. The organic and the aqueous layer were separated, and the latter was extracted with CH2Cl2 (3*30 mL). The combined organic layers were dried (Na2SO4), filtered, and concentrated in vacuo. The residue was purified by flash silica column chromatography (pure heptanes) to yield 15a as a white solid (9.1 g, 84%). The spectroscopic data were identical with those reported.<ce-sup primary_key="ce-sup-35854493-none">17,18
80%	With bromine; In chloroform; at 20℃; for 24h;	Chloroform (200 mL) was used to dissolve benzo[b]thiophene(140 mmol) followed by drop wise addition of Br2 (310 mmol). The mixture was stirred at room temperaturefor 24 h. Washing of the resultant solution was done withNa2S2O3 aqueous solution and organic layer was separatedby using ethyl acetate. It was dried and concentrated withanhydrous MgSO4. The product was re-precipitated usingn-hexane in excess which resulted in the formation of whitecolored product.
16.5 g (57 mmol, 28%)	With bromine; In chloroform;	A. 2,3-Dibromobenzo[b]thiophene STR16 Benzothiophene (26.8 g, 0.2 mol) was dissolved in 150 mL CHCl3 and treated with a solution of bromine (64 g, 0.4 mol) in 75 mL CHCl3 dropwise over an hour. The reaction was allowed to stir overnight then cautiously quenched with saturated aqueous Na2 CO3 until no gas evolution was evident. The layers were separated and the organic layer was first washed with saturated aqueous Na2 CO3 then with water. It was dried over MgSO4 and concentrated under vacuum to a solid. Recrystallized from MeOH to obtain 16.5 g (57 mmol, 28%) of a white fluffy solid. 1 H NMR (CDCl3) δ7.77-7.71 (m, 2H), 7.46-7.38 (m, 2H).
	With bromine; In chloroform;	A. Preparation of 2,3-dibromobenzo[b]thiophene. A solution of 64 g of bromine in 50 ml of chloroform was added to a solution of 26.8 g of 1-benzothiophene in 150 ml of chloroform. After stirring for approximately 18 hours, the reaction mixture was washed sequentially with 0.1N sodium hydroxide, 0.1N aqueous sodium thiosulfate, and water. The organic layer was dried over magnesium sulfate and evaporated to dryness. The residue was crystallized twice from methanol to provide 20.54 g of the desired subtitled intermediate, m.p. 57-59 C. Analysis for C8 H4 Br2 S; Calculated: C, 32.91; H, 1.38; Found: C, 32.72; H, 1.49.
16.5 g (57 mmol, 28%)	With bromine; In CHCl3and; CHCl3dropwise;	A. 2,3-Dibromobenzo[b]thiophene. Benzothiophene (26.8 g, 0.2 mol) was dissolved in 150 mL CHCl3and treated with a solution of bromine (64 g, 0.4 mol) in 75 mL CHCl3dropwise over an hour. The reaction was allowed to stir overnight then cautiously quenched with saturated aqueous Na2CO3until no gas evolution was evident. The layers were separated and the organic layer was first washed with saturated aqueous Na2CO3then with water. It was dried over MgSO4and concentrated under vacuum to a solid. Recrystallized from MeOH to obtain 16.5 g (57 mmol, 28%) of a white fluffy solid. 1H NMR (CDCl3) δ 7.77-7.71 (m, 2H), 7.46-7.38 (m, 2H).

References: [1]Patent: JP2017/160159,2017,A .Location in patent: Paragraph 0049.
[2]Patent: US2014/256936,2014,A1 .Location in patent: Paragraph 0229.
[3]Organic Letters,2017,vol. 19,p. 2564 - 2567.
[4]Chemistry - A European Journal,2014,vol. 20,p. 16266 - 16272.
[5]Chemistry - An Asian Journal,2015,vol. 10,p. 1725 - 1730.
[6]Journal of Organic Chemistry,1993,vol. 58,p. 4360 - 4369.
[7]Tetrahedron,1997,vol. 53,p. 15515 - 15534.
[8]Journal of the American Chemical Society,2018,vol. 140,p. 6432 - 6440.
[9]Chemistry - A European Journal,2019,vol. 25,p. 3582 - 3590.
[10]Chemistry - A European Journal,2013,vol. 19,p. 3721 - 3728.
[11]Dyes and Pigments,2014,vol. 111,p. 116 - 123.
[12]Tetrahedron,2013,vol. 69,p. 160 - 173.
[13]Journal of Organic Chemistry,2020,vol. 85,p. 4672 - 4681.
[14]Tetrahedron Letters,2006,vol. 47,p. 2887 - 2891.
[15]Inorganic Chemistry,2011,vol. 50,p. 8516 - 8523.
[16]Medicinal Chemistry Research,2020.
[17]Synlett,2009,p. 2691 - 2695.
[18]Chemische Berichte,1955,vol. 88,p. 34,36.
[19]Synlett,2002,p. 2083 - 2085.
[20]Patent: US6133262,2000,A .
[21]Patent: US4659717,1987,A .
[22]Patent: EP997460,2000,A1 .
[23]Heterocyclic Communications,2010,vol. 16,p. 241 - 244.
[24]New Journal of Chemistry,2014,vol. 38,p. 5754 - 5760.
[25]Patent: WO2015/188790,2015,A1 .Location in patent: Page/Page column 22.

2
[ 6287-82-7 ]
[ 917-92-0 ]
[ 221103-93-1 ]

References: [1]Chemische Berichte,1994,vol. 127,p. 247 - 260.

3
[ 6287-82-7 ]
[ 2009-97-4 ]
2-[2,3-Dibromo-1λ⁴-benzo[b]thiophen-(1E)-ylidene]-3-oxo-butyric acid ethyl ester [ No CAS ]

References: [1]Tetrahedron,1991,vol. 47,p. 8611 - 8620.

4
[ 6287-82-7 ]
[ 6773-29-1 ]
2-(2,3-Dibromo-1λ⁴-benzo[b]thiophen-1-ylidene)-malonic acid dimethyl ester [ No CAS ]

References: [1]Tetrahedron,1991,vol. 47,p. 8611 - 8620.

5
[ 6287-82-7 ]
[ 74-88-4 ]
[ 10243-15-9 ]

References: [1]Journal of the American Chemical Society,2018,vol. 140,p. 6432 - 6440.
[2]Journal of the Chemical Society. Perkin transactions I,1990,p. 1083 - 1090.

6
[ 6287-82-7 ]
[ 188002-93-9 ]

Yield	Reaction Conditions	Operation in experiment
90%	With n-butyllithium; In tetrahydrofuran; at -78℃; for 1h;	The compound <strong>[6287-82-7]2,3-dibromobenzo[b]thiophene</strong> (50.0 g, 171.1 mmole) was mixed with 1000 ml of dry THF. To the mixture, 82.0 ml of N-butyllithium (205.0 mmol) was added at -78 C. and the mixture was stirred for 1 h. After the reaction finished, 32.0 g (240.0 mmol) of Copper(II) Chloride was added and the mixture was stirred 16 h. The solution was extracted with ethyl acetate and water. The organic layer was dried with anhydrous magnesium sulfate and then the solvent was evaporated under reduced pressure. The residue was purified by column chromatography on silica to give product (32.6 g, 90%) as a purple brown solid.

References: [1]Organic Letters,2009,vol. 11,p. 3358 - 3361.
[2]Patent: US2021/40112,2021,A1 .Location in patent: Paragraph 0057-0058.
[3]New Journal of Chemistry,2014,vol. 38,p. 5754 - 5760.
[4]Helvetica Chimica Acta,1997,vol. 80,p. 111 - 120.
[5]Chemistry - A European Journal,2008,vol. 14,p. 9878 - 9889.
[6]Journal of Physical Chemistry A,2011,vol. 115,p. 225 - 231.

7
[ 6287-82-7 ]
[ 100379-00-8 ]
[ 433222-68-5 ]

References: [1]Synthesis,2002,p. 213 - 216.

8
[ 6287-82-7 ]
[ 100379-00-8 ]
2,3-bis(2,6-dimethylphenyl)benzo[b]thiophene [ No CAS ]

References: [1]Synthesis,2002,p. 213 - 216.

9
[ 6287-82-7 ]
[ 23112-96-1 ]
3-bromo-2-(2,6-dimethoxy)phenylbenzo[b]thiophene [ No CAS ]

References: [1]Synthesis,2002,p. 213 - 216.

10
[ 6287-82-7 ]
[ 23112-96-1 ]
2,3-bis(2,6-dimethoxyphenyl)benzo[b]thiophene [ No CAS ]

References: [1]Synthesis,2002,p. 213 - 216.

11
[ 6287-82-7 ]
[ 98-80-6 ]
[ 22751-52-6 ]

Yield	Reaction Conditions	Operation in experiment
80%	With tetrakis(triphenylphosphine) palladium(0); sodium carbonate; In toluene; at 130℃; for 48h;Inert atmosphere;	<strong>[6287-82-7]2,3-dibromobenzo[b]thiophene</strong> (6.3 g, 21.6 mmol), phenylboronic acid (5.5 g, 45.3 mmol), tetrakis(triphenylphosphine)palladium(0) (0.6 g, 0.5 mmol), and 1.0M Na2CO3 (86 ml) in 220 ml of toluene was stirred at 130C for 48h under nitrogen atmosphere. After the reaction had finished, the mixture was washed three times with distilled water and extracted with chloroform. The organic layer was separated, dried over anhydrous magnesium sulfate, and evaporated under reduced pressure. The crude product was purified by silica gel column chromatography using n-hexane-toluene (5:1) eluent to afford ( 4) a white powder, yield 80%. 1H NMR (CDCl3, 400MHz) 7.90-7.88 (dd, J=6.4Hz, 1H), 7.62-7.59 (dd, J=7.6Hz, 1H), 7.41-7.32 (m, 10H), 7.25-7.24 (d, J=2Hz, 2H) ppm

References: [1]Synthesis,2002,p. 213 - 216.
[2]Angewandte Chemie - International Edition,2015,vol. 54,p. 10234 - 10238.
Angew. Chem.,2015,vol. 127,p. 10372 - 10376,5.
[3]Dyes and Pigments,2014,vol. 111,p. 116 - 123.

12
[ 415680-02-3 ]
[ 6287-82-7 ]

References: [1]Journal of Organic Chemistry,2002,vol. 67,p. 1905 - 1909.

13
[ 415680-02-3 ]
[ 6287-82-7 ]
[(E)-1,2-Dibromo-2-(2-methylsulfanyl-phenyl)-vinyl]-trimethyl-silane [ No CAS ]

References: [1]Journal of Organic Chemistry,2002,vol. 67,p. 1905 - 1909.
[2]Journal of Organic Chemistry,2002,vol. 67,p. 1905 - 1909.

14
[ 21554-43-8 ]
[ 6287-82-7 ]
2-(3-bromo-1-benzothiophen-2-yl)-1,3-benzothiazole [ No CAS ]

References: [1]Russian Chemical Bulletin,2001,vol. 50,p. 2420 - 2423.
[2]Dyes and Pigments,2019,vol. 166,p. 410 - 415.

15
[ 6287-82-7 ]
[ 33513-42-7 ]
[ 10135-00-9 ]

References: [1]Journal of Heterocyclic Chemistry,2006,vol. 43,p. 101 - 109.
[2]Journal of the American Chemical Society,2018,vol. 140,p. 6432 - 6440.
[3]Synthesis,2007,p. 2135 - 2144.
[4]Synlett,2002,p. 2083 - 2085.
[5]Patent: WO2015/188790,2015,A1 .Location in patent: Page/Page column 23.

16
[ 6287-82-7 ]
[ 536-74-3 ]
[ 936800-12-3 ]

References: [1]Chemistry - A European Journal,2007,vol. 13,p. 3113 - 3119.
[2]Advanced Synthesis and Catalysis,2011,vol. 353,p. 331 - 336.
[3]Advanced Synthesis and Catalysis,2017,vol. 359,p. 1402 - 1406.
[4]Journal of the American Chemical Society,2021,vol. 143,p. 4879 - 4885.
[5]Tetrahedron Letters,2004,vol. 45,p. 1155 - 1158.

17
[ 6287-82-7 ]
[ 86134-28-3 ]
[ 768386-38-5 ]

References: [1]Organic and Biomolecular Chemistry,2004,vol. 2,p. 1413 - 1418.

18
[ 6287-82-7 ]
[ 1859-70-7 ]
<i>N</i>-{2-[(3-bromo-[2,3']bi[benzo[<i>b</i>]thiophenyl]-2'-yl)-acetyl]-phenyl}-4-methyl-benzenesulfonamide [ No CAS ]

References: [1]Tetrahedron,2007,vol. 63,p. 690 - 702.

19
[ 95-15-8 ]
[ 6287-82-7 ]
(R,R) [3,4-bis(2',5'-dimethylphospholanyl)]-benzo[b]thiophene [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
90%	With sodium hydroxide; bromine; In chloroform;	Synthesis of (R,R) [3,4-bis(2',5'-dimethylphospholanyl)]-benzo[b]thiophene Stage a: Synthesis of 2,3-dibromo-benzo[b]thiophene A solution of Br2(21.1 mL) in CHCl3 (65 mL) was dropped into a solution of benzo[b]thiophene (26.4 g) in CHCl3 (120 mL), under stirring, at a temperature of 0 C. The progress of the reaction was controlled in TLC (hexane) up to the disappearance of the starting product: Rf (thianaphthene): 0.33, Rf (2,3-dibromobenzothiophene): 0.5. The mixture was then poured into aqueous, NaOH; the organic phase was separated, washed twice with a solution of 10% NaOH and once with water, and then dehydrated on Na2SO4. The solvent was evaporated to yield the 2,3-dibromo-benzo[b]thiophene as a white solid (52 g) (yield 90%).

References: [1]Patent: US2005/107248,2005,A1 .

20
[ 868851-44-9 ]
[ 6287-82-7 ]
(1R)-3-bromo-2-{3⁽²⁾-bromo[b]benzothien-2⁽³⁾-yl}bornylene [ No CAS ]

References: [1]Russian Journal of Organic Chemistry,2007,vol. 43,p. 747 - 752.

21
[ 6287-82-7 ]
[ 714275-73-7 ]

References: [1]Organic and Biomolecular Chemistry,2004,vol. 2,p. 1413 - 1418.

22
[ 6287-82-7 ]
[ 714275-74-8 ]

References: [1]Organic and Biomolecular Chemistry,2004,vol. 2,p. 1413 - 1418.

23
[ 6287-82-7 ]
C₂₀H₁₅OS⁽¹⁺⁾*BF₄^(1-) [ No CAS ]

References: [1]Organic and Biomolecular Chemistry,2004,vol. 2,p. 1413 - 1418.

24
[ 6287-82-7 ]
C₂₁H₁₇OS⁽¹⁺⁾*BF₄^(1-) [ No CAS ]

References: [1]Organic and Biomolecular Chemistry,2004,vol. 2,p. 1413 - 1418.

25
[ 33775-94-9 ]
[ 6287-82-7 ]

References: [1]Journal of Organic Chemistry,2002,vol. 67,p. 1905 - 1909.
[2]Journal of Organic Chemistry,2002,vol. 67,p. 1905 - 1909.

26
[ 6287-82-7 ]
[ 77-78-1 ]
[ 10243-15-9 ]

Yield	Reaction Conditions	Operation in experiment
	With hydrogenchloride; n-butyllithium; In diethyl ether; hexane;	A. Preparation of 2-methyl-3-bromobenzo[b]thiophene. To a solution of 15.88 g of <strong>[6287-82-7]2,3-dibromobenzo[b]thiophene</strong> in 150 ml of dry diethyl ether at 0 C. was added a solution of 20 ml of diethyl ether and 34 ml of a 1.6M solution of n-butyl lithium in hexane. After stirring for one hour at 0 C., a solution of 10.2 ml of dimethylsulfate in 20 ml of diethyl ether was added and the reaction was stirred at 0 C. for 4 hours. The mixture was allowed to warm to room temperature. After the addition of 125 ml of 1N hydrochloric acid, the reaction mixture was stirred for 15 minutes. The layers were separated and the aqueous layer was extracted with diethyl ether. The combined ether extracts were dried over magnesium sulfate and evaporated in vacuo giving an oil. The oil was cooled and it solidified. The resulting crystals were recovered by filtration providing 8.7 g of the desired subtitled intermediate, m.p. 39-40 C. Analysis for C9 H7 BrS; Calculated: C, 47.59; H, 3.11; Found: C, 48.77; H, 2.80.

References: [1]Patent: US4659717,1987,A .

27
[ 6287-82-7 ]
[ 624-92-0 ]
3-bromo-2-(methylthio)benzo[b]thiophene [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	With hydrogenchloride; n-butyllithium; In diethyl ether; hexane;	B. Preparation of 3-bromo-2-(methylthio)benzo[b]thiophene. A solution of 8.76 g of <strong>[6287-82-7]2,3-dibromobenzo[b]thiophene</strong> in 75 ml of diethyl ether was cooled to 0 C. and 19 ml of a 1.6M solution of n-butyl lithium in hexane and 10 ml of diethyl ether were added. A pink slurry formed which was stirred for one hour. A solution of 2.7 ml of methyl disulfide in 10 ml of diethyl ether was added and the reaction mixture was stirred for 4 hours at 0 C. Approximately 100 ml of 1N hydrochloric acid were added and the reaction was allowed to warm to room temperature. The layers were separated and the aqueous layer was extracted with diethyl ether. The combined organic extracts were dried over magnesium sulfate and evaporated to dryness. The resulting oil was vacuum distilled at 1.5 torr providing 1 g of the desired subtitled intermediate. Analysis for C9 H7 BrS2; Calculated: C, 41.71; H, 2.72; S, 25.00; Found: C, 42.00; H, 3.02; S, 24.74.

References: [1]Patent: US4659717,1987,A .

28
[ 102-54-5 ]
[ 6287-82-7 ]
[ 7646-85-7 ]
[ 926885-52-1 ]

References: [1]Journal of Organometallic Chemistry,2007,vol. 692,p. 60 - 69.

29
[ 102-54-5 ]
[ 6287-82-7 ]
[ 7646-85-7 ]
[ 887343-60-4 ]

References: [1]Journal of Organometallic Chemistry,2007,vol. 692,p. 60 - 69.

30
[ 14282-76-9 ]
[ 6287-82-7 ]
[ 1047655-25-3 ]

References: [1]Organic Letters,2008,vol. 10,p. 3639 - 3642.

31
[ 6287-82-7 ]
[ 7646-85-7 ]
[ 1186585-06-7 ]

Yield	Reaction Conditions	Operation in experiment
		To a 100 ml Schlenk reaction vessel were added under a nitrogen atmosphere 886 mg (3.03 mmol) of <strong>[6287-82-7]2,3-dibromobenzothiophene</strong> (manufactured by Sigma-Aldrich) and 8 ml of THF. The solution was cooled to -30C and 3.8 ml (3.0 mmol) of a THF solution of isopropylmagnesium bromide (manufactured by Tokyo Chemical Industry Co. Ltd., 0.80M) was added dropwise. After 30 minutes of aging, the whole was cooled to -50C and 3.0 ml (3.0 mmol) of a diethyl ether solution of zinc chloride (manufactured by Sigma-Aldrich, 1.0M) was added dropwise at the temperature. After the temperature was gradually raised to room temperature, the formed white slurry liquid was concentrated under reduced pressure. To the obtained white solid [(3-bromobenzothienyl-2-zinc chloride) (compound of the formulae (6) and (7))] were added 492 mg (1.01 mmol) of 1,4-dibromo-2,5-diiodobenzene synthesized in Synthetic Example 1 (compound of the formula (5)), 91.7 mg (0.079 mmol) of tetrakis(triphenylphosphine)palladium (manufactured by Tokyo Chemical Industry Co. Ltd.) as a catalyst, and 8 ml of THF. After the reaction was carried out at 63C for 10 hours, the vessel was cooled with water and the reaction was stopped by adding 4 ml of 1N hydrochloric acid. Toluene was added, the obtained suspension was filtrated, and the solid on the filter plate was washed with toluene and water. The solid was dried under reduced pressure to obtain 292 mg of a white solid. On the other hand, the filtrate was subjected to phase separation and the organic phase was washed with water. The organic phase was concentrated under reduced pressure and the solvent was removed by evaporation. The obtained solid was washed with hexane (10 ml) and the residue was recrystallized from toluene. After the precipitated crystals were dried under reduced pressure, 206 mg of a white solid was obtained. The objective product was obtained in 75% yield together with the white solid after the previous filtration. 1H-NMR (CDCl3, 21C): δ=7.95-7.84 (m, 4H), 7.81 (s, 2H), 7.58-7.44 (m, 4H). MS m/z: 658 (M+, 44%), 498 (M+-2Br, 34), 338 (M+-4Br, 100), 306 (M+-4Br-S), 9), 169 (M+-4Br)/2, 66).

References: [1]Patent: EP2067782,2009,A1 .Location in patent: Page/Page column 25.

32
[ 6287-82-7 ]
[ 1101752-38-8 ]

References: [1]Organic Letters,2009,vol. 11,p. 3358 - 3361.
[2]Patent: US2021/40112,2021,A1 .

33
[ 6287-82-7 ]
[ 5565-85-5 ]
[ 201-69-4 ]