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Cena, Nicolas ; Blanski, Rusty L. ; Quintana, Ashlee S. , et al. DOI:

Abstract: First reported in 1966-1967, the compound tri(2-ethylhexyl)phosphine appears to be a hidden gem for ionic liquids Although this compound offers many potential intriguing properties that are inherent due to its branching and diastereomeric nature, there is only a single report employing this material as an ionic liquid constituent. Through quaternization and anion exchange, a total of 24 new room temperature ionic liquids were prepared containing bromide (Br-), bis(trifluoromethanesulfonyl)imide (Tf2N-), hexafluorophosphate (PF-6), and tetrafluoroborate (BF-4) anions. In addition to the usual anal. methods, the compounds phys. properties such as d., solubility, viscosity, and surface tension were probed to ascertain their suitability for aerospace applications. Differential scanning calorimetry (DSC) and thermogravimetric anal. (TGA) were employed to study the thermal behavior of the materials focusing on phase transitions and degradation behavior. Remarkably, all ionic liquids prepared in this study are liquids at room temperature with relatively low viscosities and are soluble in many common organic solvents. Structure-property relationships were assessed, particularly focusing on the effect that the chain length appendage and/or anion type has on a given phys. property. An updated synthetic procedure and characterization of the tri(2-ethylhexyl)phosphine starting material are provided. A new synthesis procedure for the starting material silver(I) tetrafluoroborate is also reported.

Keywords: Room temperature ionic liquid ; Phosphonium cation ; DSC ; TGA ; Diastereomer mixture ; Branched alkane

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Product Details of [ 18908-66-2 ]

CAS No. :18908-66-2 MDL No. :MFCD00000220
Formula : C8H17Br Boiling Point : -
Linear Structure Formula :- InChI Key :NZWIYPLSXWYKLH-UHFFFAOYSA-N
M.W : 193.12 Pubchem ID :86804
Synonyms :

Calculated chemistry of [ 18908-66-2 ]      Expand+

Physicochemical Properties

Num. heavy atoms : 9
Num. arom. heavy atoms : 0
Fraction Csp3 : 1.0
Num. rotatable bonds : 5
Num. H-bond acceptors : 0.0
Num. H-bond donors : 0.0
Molar Refractivity : 48.44
TPSA : 0.0 Ų

Pharmacokinetics

GI absorption : Low
BBB permeant : Yes
P-gp substrate : No
CYP1A2 inhibitor : No
CYP2C19 inhibitor : No
CYP2C9 inhibitor : No
CYP2D6 inhibitor : No
CYP3A4 inhibitor : No
Log Kp (skin permeation) : -4.27 cm/s

Lipophilicity

Log Po/w (iLOGP) : 2.93
Log Po/w (XLOGP3) : 4.52
Log Po/w (WLOGP) : 3.6
Log Po/w (MLOGP) : 3.76
Log Po/w (SILICOS-IT) : 3.13
Consensus Log Po/w : 3.59

Druglikeness

Lipinski : 0.0
Ghose : None
Veber : 0.0
Egan : 0.0
Muegge : 2.0
Bioavailability Score : 0.55

Water Solubility

Log S (ESOL) : -3.55
Solubility : 0.0538 mg/ml ; 0.000279 mol/l
Class : Soluble
Log S (Ali) : -4.24
Solubility : 0.0111 mg/ml ; 0.0000573 mol/l
Class : Moderately soluble
Log S (SILICOS-IT) : -3.58
Solubility : 0.0506 mg/ml ; 0.000262 mol/l
Class : Soluble

Medicinal Chemistry

PAINS : 0.0 alert
Brenk : 1.0 alert
Leadlikeness : 2.0
Synthetic accessibility : 3.81

Safety of [ 18908-66-2 ]

Signal Word:Warning Class:
Precautionary Statements:P501-P210-P264-P280-P302+P352-P370+P378-P337+P313-P305+P351+P338-P362+P364-P332+P313-P403+P235 UN#:
Hazard Statements:H315-H319-H227 Packing Group:
GHS Pictogram:

Application In Synthesis of [ 18908-66-2 ]

* All experimental methods are cited from the reference, please refer to the original source for details. We do not guarantee the accuracy of the content in the reference.

  • Upstream synthesis route of [ 18908-66-2 ]
  • Downstream synthetic route of [ 18908-66-2 ]

[ 18908-66-2 ] Synthesis Path-Upstream   1~18

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  • [ 996-82-7 ]
  • [ 16493-80-4 ]
Reference: [1] Journal of the American Chemical Society, 1936, vol. 58, p. 1872
[2] Hoppe-Seyler's Zeitschrift fuer Physiologische Chemie, 1942, vol. 274, p. 180
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  • [ 18908-66-2 ]
  • [ 16493-80-4 ]
Reference: [1] Hoppe-Seyler's Zeitschrift fuer Physiologische Chemie, 1951, vol. 288, p. 69,71
  • 3
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  • [ 88-99-3 ]
  • [ 117-81-7 ]
Reference: [1] Synthesis, 1985, # 1, p. 40 - 45
  • 4
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  • [ 1185885-86-2 ]
YieldReaction ConditionsOperation in experiment
87.4% With potassium carbonate In N,N-dimethyl-formamide at 145℃; for 15 h; 3,6dimethylformamide (DMF) in 250 ml dithiol2yl2,5dihydropyrrolo[3,4c]pyrrole1,4dione(3,6Dithiophen2yl2,5dihydropyrrolo[3,4c]pyrrole1,4dione,put 13.0 g, 43.3 mmol) and potassium carbonate (K2CO3, 24.0g) was added at atemperature of 145 ° c good It was dissolved. The 2ethylhexylbromide (2ethylhexylbromide,38.6g, 200mmol) was put in the solution at a time by using a syringe. 145Stirred over 15 hours at ° C and then lowered to room temperature and stirred to give poured over 500ml of cold water andgives the filter washed several times with water and alcohol. After drying, the silica column (silica column, eluent Hexane:Methylene chloride = 1: 10) through a solid was obtained of a dark purple powder.
79% With potassium carbonate In N,N-dimethyl-formamide at 140℃; for 12 h; Inert atmosphere Under a nitrogen atmosphere, 3,6-dithiophen-2-yl-2,5-dihydropyrrolo [3,4-c] pyrrole-1,4-dione (13 g, 43.3 mmol) dissolved in 300 mL of dimethylformamide (DMF) was added to a 500 ml two-necked round bottom flask. After stirring the mixture with heating, potassium carbonate (K2CO3) (4 eq.) was added and stirred at 140°C. Then, 2-ethylhexylbromomide (4.6 eq.) was added thereto and stirred for 12 hours. After stopping the reaction by thin film chromatography (TLC) confirmation, the resulting mixture was washed with ice water and solids were filtered through a filter and purified by silica column eluted with chloroform to obtain 2,5-diethylhexyl-3,6-dithiophen-2-ylpyrrolo[3,4-c]pyrrole-1,4-dione (18.01 g, Y=79percent).
72% With 18-crown-6 ether; potassium carbonate In N,N-dimethyl-formamide at 120 - 150℃; for 12 h; Inert atmosphere in a nitrogen atmosphere of formula (5) Compound 5 (3. 00g, 9. 99mmol), anhydrous potassium carbonate (6. 22g, 45mmol) was added to a solution containing 50ml N, N- dimethylformamide (DMF ) the reaction flask was heated to 120 ° C, and then dissolved in a minimum of DMF of 1-bromo-2-ethylhexanoate was added dropwise to the burning reaction flask while adding a small amount of 18-crown-6 ether, dropwise after the addition is complete warm to 150 ° C, for 12 hours. Then cooled to room temperature, the reaction solution was poured into four volumes of distilled water, the aqueous phase was extracted with methylene chloride to colorless, and then the organic phase was washed three times with distilled water, the organic solvent was removed under reduced pressure after boiling range 60 ° C -90 ° C petroleum ether as eluent over a silica gel column, to give the formula shown in (5) compound 6 3. 77g, yield 72percent. ;
63%
Stage #1: With potassium carbonate In N,N-dimethyl-formamide at 145℃; for 0.166667 h;
Stage #2: at 100 - 145℃;
3,6-Dithiophen-2-yl-2,5-dihydropyrrolo[3,4-c]pyrrole-1,4-(2H,5H)-dione (cmpd describedhere above)(3.922 g, 13.06 mmol) and potassium carbonate (7.226 g, 52.28 mmol,4 equiv) were dried under vacuum. DMF (65 mL) was added and the medium was stirredat 145 °C for 10 min resulting in a deeper purple color medium. 2-Ethylhexylbromide (11.6 mL, 65.23 mmol,5 equiv) was added slowly at 100 °C. The medium was stirred further at 145 °C overnight, then cooled to rt.The reaction medium was quenched with an ice/water solution (150 mL), then extracted with CH2Cl2 andwashed with water, finally dried with brine and over Na2SO4. Purification by column chromatography onsilica using a gradient of CH2Cl2/petroleum ether as eluent (50/50 to 100/0) afforded cmpd 1 as a purple solid(4.336 g, 63percent).
52.4% With potassium carbonate In N,N-dimethyl-formamide at 70℃; Charge a 500-ml eggplant-shape flask with the above- prepared compound (a) (5.0 g, 13.3 mmol), 2-ethylhexyl bromide (8.0 g, 41.6 mmol), dry DMF (100 ml), and potassium carbonate (6.0 g). Agitate the flask content all night long at 70° C. Afier distilling the solvent away under reduced pressures, add a mixed solvent of methanol and water (MeOH/water=1/1, 100 ml) to the flask. Separate the precipitate by filtration and purify it by a silica gel colunm chromatography (solvent: toluene). Thus, a red powder (4.5g, 52.4percent) is obtained. mlz=525.3 (M+H)
51% With potassium carbonate In N,N-dimethyl-formamide at 120℃; for 24 h; The compound 1 (10.0g, 33.3mmol), 2- ethylhexyl bromide ( 19. 3g, 99.9mmol), and K2CO3 (18.4g, 133mmol) dry DIt was mixed in MF (300mL), stirred for 24 hours at 120. ° C. . After cooling to room temperature , precipitationThe reaction mixture was poured into a large amount of ice water to form a palace compound . The resulting precipitate was times by filtrationTo yield , and washed with water and methanol .The resulting product was purified by silica gel column chromatography ( eluent : CHCl3 / hexaDown = 1: 1, v purified on / v ) , then recrystallized from CHCl3 / methanol , and dried under vacuumTo give compound 2 as a red- brown solid ( 8.89 g , yield = 51percent ) .
25%
Stage #1: at 119.84℃; for 0.5 h; Inert atmosphere
Stage #2: at 129.84 - 139.84℃; Inert atmosphere
Compound 2(3.36 g, 10.8 mmol) and 100 mL of dry DMF were added to a 250 mL two-neck round–bottom flask, equipped with a condenserand stir-bar and placed under N2 atmosphere. The mixturewas heated to 393 K, stirred for 30 min, and 2-ethylhexylbromide (6.05 g, 31.3 mmol) was then addedquickly (while at 393 K).The reaction mixture was subsequently stirred at 413 K forca. 6 h, and cooled to room temperature. The organic phasewas extracted with diethyl ether and washed with water. Thediethyl ether was evaporated, and the resulting tacky solid(red) was purified by column chromatography using CHCl3as eluent. 1.30 g of 3 was isolated (25 percent yield). 1H NMR(500MHz, CDCl3): (ppm) = 8.33 (d, J = 3.6 Hz, 2 H), 7.61 (d,J = 1.3 Hz, 2 H), 6.69 (dd, J = 1.7 Hz, 3.6 Hz, 2 H), 4.04 (d,J = 7.8 Hz, 4 H), 1.80–1.68 (m, 2 H), 1.39–1.26 (m, 16 H), 0.95–0.85 (m, 12 H). 13C (75 MHz, CDCl3): (ppm) = 161.4,145.0, 144.8, 134.1, 120.4, 113.6, 106.6, 46.3, 40.1, 30.7,28.8, 24.0, 23.2, 14.2, 10.9.
24%
Stage #1: With potassium carbonate In N,N-dimethyl-formamide at 120℃; for 1 h; Inert atmosphere
Stage #2: at 120℃; for 24 h; Inert atmosphere
General procedure: This compound was synthesized according to a literature procedure [41] 3,6-Di(thiophen-2-yl)pyrrolo[3,4-c]pyrrole-1,4(2H,5H)-dione (3) (0.45 g, 1.5 mmol) and K2CO3 (0.83 g, 6.0 mmol) were added to the reaction vessel. The reaction vessel was fitted with a silicon septum, evacuated, and back-filled with argon. This sequence was repeated twice. Anhydrous DMF (16 mL) was added under a stream of argon, and the resulting mixture was stirred at 120 °C for 1 h. Then, 1-iodooctane (4a) (1.44 g, 6.0 mmol) was added in one portion, and the mixture was stirred at 120 °C for 24 h. After cooling to room temperature, the reaction mixture was poured into ice-cold water (100 mL), and extracted with CH2Cl2 (4 x 25 ml). The organic fractions were collected, dried over Na2SO4, filtered, and concentrated at reduced pressure. The residue was purified by flash chromatography on silica gel with a mixture of CH2Cl2 and petroleum ether (1:1) as eluent. The chromatographic fractions containing the required compound were collected and concentrated at reduced pressure to give 1a as a dark pink solid (0.46 g, 58percent yield)

Reference: [1] Patent: KR2015/48636, 2015, A, . Location in patent: Paragraph 0499-0502
[2] Patent: KR101676526, 2016, B1, . Location in patent: Paragraph 0194-0196
[3] Journal of Materials Chemistry, 2012, vol. 22, # 16, p. 7945 - 7953
[4] RSC Advances, 2016, vol. 6, # 11, p. 9023 - 9036
[5] Patent: CN103360397, 2016, B, . Location in patent: Paragraph 0031-0033; 0035
[6] RSC Advances, 2014, vol. 4, # 101, p. 58027 - 58035
[7] Synlett, 2015, vol. 26, # 15, p. 2109 - 2116
[8] Patent: US9590187, 2017, B2, . Location in patent: Page/Page column 39; 40
[9] Patent: JP2015/196661, 2015, A, . Location in patent: Paragraph 0070-0074
[10] Collection of Czechoslovak Chemical Communications, 2012, vol. 77, # 6, p. 462 - 469
[11] Journal of Polymer Science, Part A: Polymer Chemistry, 2014, vol. 52, # 16, p. 2356 - 2366
[12] Dyes and Pigments, 2012, vol. 95, # 1, p. 126 - 133
[13] European Journal of Organic Chemistry, 2013, # 23, p. 5076 - 5084
[14] Chemical Communications, 2014, vol. 50, # 31, p. 4099 - 4101
[15] Journal of Fluorescence, 2016, vol. 26, # 6, p. 1939 - 1949
[16] Dyes and Pigments, 2016, vol. 135, p. 154 - 162
[17] Journal of Materials Chemistry A, 2015, vol. 3, # 8, p. 4229 - 4238
[18] Advanced Functional Materials, 2013, vol. 23, # 28, p. 3519 - 3524
[19] European Journal of Organic Chemistry, 2017, vol. 2017, # 33, p. 4896 - 4904
[20] RSC Advances, 2015, vol. 5, # 25, p. 19520 - 19527
[21] Patent: WO2008/664, 2008, A1, . Location in patent: Page/Page column 43
[22] Patent: WO2009/47104, 2009, A2, . Location in patent: Page/Page column 33; 34
[23] Journal of Polymer Science, Part A: Polymer Chemistry, 2010, vol. 48, # 7, p. 1669 - 1675
[24] Journal of the American Chemical Society, 2010, vol. 132, # 44, p. 15547 - 15549
[25] Chemistry of Materials, 2013, vol. 25, # 12, p. 2549 - 2556
[26] Electrochimica Acta, 2014, vol. 144, p. 211 - 220
[27] Dyes and Pigments, 2016, vol. 127, p. 37 - 44
[28] Journal of Heterocyclic Chemistry, 2017, vol. 54, # 3, p. 1983 - 1994
[29] Inorganica Chimica Acta, 2017, vol. 468, p. 192 - 202
[30] Journal of Materials Chemistry A, 2018, vol. 6, # 42, p. 20904 - 20915
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  • [ 1380497-22-2 ]
Reference: [1] Chemistry of Materials, 2012, vol. 24, # 12, p. 2364 - 2372
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  • [ 1185885-86-2 ]
  • [ 1380497-22-2 ]
Reference: [1] Journal of Materials Chemistry C, 2015, vol. 3, # 34, p. 8932 - 8941
  • 7
  • [ 18908-66-2 ]
  • [ 1000623-95-9 ]
Reference: [1] Electrochimica Acta, 2014, vol. 144, p. 211 - 220
[2] Journal of Materials Chemistry A, 2015, vol. 3, # 8, p. 4229 - 4238
[3] Patent: KR101676526, 2016, B1,
[4] European Journal of Organic Chemistry, 2017, vol. 2017, # 33, p. 4896 - 4904
  • 8
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  • [ 1000623-95-9 ]
Reference: [1] Dyes and Pigments, 2012, vol. 95, # 1, p. 126 - 133
[2] Chemistry of Materials, 2013, vol. 25, # 12, p. 2549 - 2556
[3] Collection of Czechoslovak Chemical Communications, 2012, vol. 77, # 6, p. 462 - 469
[4] Synlett, 2015, vol. 26, # 15, p. 2109 - 2116
  • 9
  • [ 18908-66-2 ]
  • [ 32281-36-0 ]
  • [ 1160823-77-7 ]
YieldReaction ConditionsOperation in experiment
87%
Stage #1: With sodium hydroxide; zinc In water at 120℃; for 13 h;
Stage #2: With tetrabutylammomium bromide In water
2.2 g of benzo [1,2-b: 4,5-b '] dithiophene-4,8-dione was weighed out in a single-Add zinc powder 1.5g,Sodium hydroxide 6 g,Distilled water 35g,Heating reflux,The oil bath temperature is controlled at 120 ° C,Reaction time: 13h;The solution quickly changed from yellow to red,As the reaction progresses,The solution was homogeneous.At this time, 5.8 g of C8H17Br and 0.11 g of catalytic equivalent of tetrabutylammonium bromide TBAB were added,As the reaction progresses, the solution changes from black to red,Eventually turned pale yellow.Terminate the reaction: add water to quench.Refining process: multiple extraction with ether, anhydrous MgSO4 dry, spin the solvent,Vacuum drying to constant weight,To give the product 4,8-bis (2-ethyl-hexyloxy) benzo [1,2-b: 4,5-b 'Dithiophene3.9 g,The yield was 87percent.
87%
Stage #1: With sodium hydroxide; zinc In water at 120℃; for 13 h;
Stage #2: With tetrabutylammomium bromide In water
2.2 g of benzo [1,2-b: 4,5-b '] dithiophene-4,8-dione In a single-necked flask, 1.5 g of zinc powder was added,Sodium hydroxide 6 g,Distilled water 35g, heated to reflux, oil bath temperature control at 120 , reaction time: 13h;The solution quickly changed from yellow to red,As the reaction progresses, the solution is homogeneous.At this time, 5.8 g of C8H17Br and 0.11 g of catalytic equivalent of tetrabutylammonium bromide TBAB were added,As the reaction progresses, the solution changes from black to red and eventually becomes pale yellow. Terminate the reaction: add water to quench.Refining process: extraction with ether several times, anhydrous MgSO4 dry, spin the solvent, vacuum drying to constant weight,The yield of the product 4,8-bis (2-ethyl-hexyloxy) benzo [1,2-b: 4,5-b '] dithiophene was obtained 3.9 g, in a yield of 87percent.Benzo [1,2-b: 4,5-b '] dithiophene-4,8-dione, RBr, zinc dust, tetrabutylammonium bromide (TBAB), sodium hydroxide, waterThe mass ratio is 1: 2.6: 0.68: 0.05: 2.7: 15.91.
65%
Stage #1: With sodium hydroxide; zinc In water for 1 h; Reflux
Stage #2: With tetrabutylammomium bromide In water for 6 h; Reflux
In a flask, 4,8-dihydrobenzo[1,2-b:4,5-b′]dithiophen-4,8-dione (6) (6.6 g, 30 mmol) and zinc powder (4.29 g, 66 mmol) were added to 90 ml of water, then 18 g of NaOH was added into the mixture. After the solution was refluxed for 1 h, 1-bromo-2-ethylhexane (17.4 g, 90 mmol) and a catalytic amount of tetrabutylammonium bromide were added and heated to reflux for another 6 h. Then, cold water (300 ml) was added and the mixture was extracted with ethyl acetate, the extract was dried over anhydrous magnesium sulfate, the residue was purified by column chromatography on silica gel to obtain 4,8-bis(2-ethylhexyloxy)benzo[1,2-b:3,4-b]dithiophene (7) in a 65percent yield. Compound 7 (6.1 g, 13.6 mmol) was added into THF (200 ml) under nitrogen, n-butyllithium (36.3 mmol, 2.2 M) was added dropwise to the mixture at −80 °C and stirred for 1 h, the cooling bath was removed, and the reactant was stirred at ambient temperature for another 1 h. Trimethyltin chloride (8 g, 40.4 mmol) was added in one portion at −80 °C and the reactant was stirred at ambient temperature overnight. After 200 ml cold water was added and the mixture was extracted with hexane, the organic layer was dried over anhydrous magnesium sulfate, after the evaporation of solvent, the residue was recrystallized by ethyl alcohol and obtained 2,6-bis(trimethyltin)-4,8-bis(2-ethylhexyl)benzo[1,2-b:3,4-b′]dithiophene 8 (6.15 g, 7.96 mmol) in a 58.3percent yield.
65%
Stage #1: With sodium hydroxide; zinc In water for 1 h; Reflux
Stage #2: With tetrabutylammomium bromide In waterReflux
To the solution of 2 (2.20 g, 10 mmol) in water (40 mL), zincpower (1.96 g, 30 mmol) and sodium hydroxide (8.00 g, 200 mmol)were added and the reaction mixture was refluxed for 1 h. To theresultant solution, catalytic amount of tetra-n-butylammoniumbromide (0.032 g, 0.1 mmol) was added followed by the addition of1-bromo-2-ethylhexane (5.79 g, 30 mmol). The reaction mixturewas refluxed overnight and then poured into water (200 mL). Themixture was extracted with diethyl ether (3 50 mL). The combinedorganic extract was dried over anhydrous Na2SO4. Solventwas removed under reduced pressure and residue was purified bysilica gel column chromatography (1:15 dichloromethane/hexaneeluent) to give the titled compound as white solid (yield 65percent).1H NMR (500 MHz, CDCl3, d ppm): 0.93 (t, J 7.0 Hz, 6H), 1.01 (t,J 7.5 Hz, 6H), 1.34e1.44 (m, 8H), 1.45e1.53 (m, 2H), 1.55e1.75 (m,6H), 1.76e1.84 (m, 2H), 4.17 (d, J 5.5 Hz, 4H), 7.36 (d, J 5.5 Hz,2H), 7.47 (d, J 5.5 Hz, 2H).
64.9%
Stage #1: With sodium hydroxide; zinc In water for 1 h; Reflux
Stage #2: With tetrabutylammomium bromide In water for 8 h; Reflux
DI water to 4,8dihydrobenzoin (H2O) in 4.60 ml [1,2b:4,5b'] dithiophene 4,8dione(4,8dehydrobenzo[l, 2b:4,5b']dithiophene4,8dione,8.0 g, 36.2 mmol) and zinc powder (Zn powder) (5.2 g, 79.6 mmol) into a stirred back, sodiumhydroxide (NaOH, stirring to 24 g) and the mixture was refluxed for 1 hour.The color of the reaction solution turned orange from yellow through red. 2ethylhexylbromide (2ethylhexylbromide,21.0 g,108.9 mmol) to the solution and to put the tetrabutylammonium bromide (tetrabutylammonium bromide, as catalyst) werestirred / reflux for 2 hours. If the solution of the red color, or a dark red color to give the addition of zinc powder (zinc powder)further stirred / reflux for 6 hours. This solution was back extracted with 2 poured into diethyl ether (Diethyl ether) times incold water, to remove the residue magnesium sulfate (MgSO4) (Magnesium sulfate). Under reduced pressure, the remainingsolution to remove the solvent, and silica column (silica column, eluent Pet ether: MC = 9: 1) through a colorless liquid.
64.9%
Stage #1: With sodium hydroxide; zinc In water for 1 h; Reflux
Stage #2: With tetrabutylammomium bromide In water for 2 h; Reflux
Stage #3: for 6 h; Reflux
Dihydrobenzo[1,2-b: 4,5-b']dithiophene-4,8-dione (8.0 g, 36.2 mmol) and zinc powder (5.2 g) were dissolved in 60 ml of distilled water G, 79.6 mmol) was added to the reaction mixture, and sodium hydroxide (24 g) was added thereto, and the mixture was refluxed for 1 hour while changing the color of the solution from yellow to red to orange. To this solution was added 2-ethylhexylbromide (21.0 g, 108.9 mmol) and tetrabutylammonium bromide (as catalyst) and stirred / refluxed for 2 hours. The color of the solution was red or dark If red was added, zinc powder was added and stirred / refluxed for 6 hours. The solution was poured into cold water, extracted twice with diethyl ether, and then the residue was removed with magnesium sulfate (MgSO4). The remaining solution was decompressed to remove the solvent, and a colorless liquid of the formula 4-b was obtained through a silica column (silica column, eluent: Pet ether: MC = 9: 1) (Yield: 64.9percent)

Reference: [1] Chemistry - A European Journal, 2015, vol. 21, # 45, p. 16252 - 16265
[2] Patent: CN105968125, 2016, A, . Location in patent: Paragraph 0094; 0095; 0096; 0097; 0152; 0153
[3] Patent: CN105968124, 2016, A, . Location in patent: Paragraph 0095; 0096; 0097; 0098
[4] Polymer, 2010, vol. 51, # 13, p. 2897 - 2902
[5] RSC Advances, 2014, vol. 4, # 49, p. 25532 - 25539
[6] Journal of the American Chemical Society, 2014, vol. 136, # 27, p. 9608 - 9618
[7] Journal of Polymer Science, Part A: Polymer Chemistry, 2010, vol. 48, # 8, p. 1822 - 1829
[8] Reactive and Functional Polymers, 2012, vol. 72, # 11, p. 897 - 903
[9] Organic Electronics: physics, materials, applications, 2016, vol. 37, p. 312 - 325
[10] Patent: KR2015/48636, 2015, A, . Location in patent: Paragraph 0477-0479
[11] Patent: KR2015/114418, 2015, A, . Location in patent: Paragraph 0475-0478
[12] Polymer, 2011, vol. 52, # 2, p. 415 - 421
[13] Journal of Polymer Science, Part A: Polymer Chemistry, 2011, vol. 49, # 16, p. 3604 - 3614
[14] Australian Journal of Chemistry, 2014, vol. 67, # 5, p. 711 - 721
[15] Macromolecules, 2011, vol. 44, # 6, p. 1414 - 1420
[16] Chemistry of Materials, 2010, vol. 22, # 9, p. 2696 - 2698
[17] Macromolecules, 2011, vol. 44, # 17, p. 6659 - 6662
[18] Macromolecules, 2012, vol. 45, # 3, p. 1710 - 1714
[19] Macromolecules, 2012, vol. 45, # 3, p. 1208 - 1216
[20] Journal of Polymer Science, Part A: Polymer Chemistry, 2014, vol. 52, # 7, p. 1028 - 1036
[21] Journal of Nanoscience and Nanotechnology, 2014, vol. 14, # 8, p. 6038 - 6042
[22] Patent: US8933441, 2015, B2, . Location in patent: Page/Page column 45
[23] Chemical Physics Letters, 2017, vol. 667, p. 254 - 259
[24] Physical Chemistry Chemical Physics, 2017, vol. 19, # 31, p. 20513 - 20522
[25] Patent: KR2018/38433, 2018, A, . Location in patent: Paragraph 0215-0219
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  • [ 1160823-77-7 ]
Reference: [1] Chemical Communications, 2010, vol. 46, # 27, p. 4997 - 4999
[2] Journal of Polymer Science, Part A: Polymer Chemistry, 2013, vol. 51, # 5, p. 1051 - 1057
  • 11
  • [ 18908-66-2 ]
  • [ 32281-36-0 ]
  • [ 1160823-78-8 ]
Reference: [1] Macromolecules, 2013, vol. 46, # 19, p. 7920 - 7931
[2] Journal of Polymer Science, Part A: Polymer Chemistry, 2014, vol. 52, # 7, p. 1028 - 1036
[3] Journal of the American Chemical Society, 2014, vol. 136, # 27, p. 9608 - 9618
[4] Patent: KR2015/48636, 2015, A,
[5] Physical Chemistry Chemical Physics, 2017, vol. 19, # 31, p. 20513 - 20522
  • 12
  • [ 18908-66-2 ]
  • [ 1160823-78-8 ]
Reference: [1] Patent: US8933441, 2015, B2,
[2] Organic Electronics: physics, materials, applications, 2016, vol. 37, p. 312 - 325
[3] Patent: KR2015/114418, 2015, A,
[4] Patent: KR2018/38433, 2018, A,
  • 13
  • [ 18908-66-2 ]
  • [ 1147124-21-7 ]
  • [ 1147124-23-9 ]
YieldReaction ConditionsOperation in experiment
90% With potassium carbonate In N,N-dimethyl-formamide at 100℃; for 15 h; Inert atmosphere In a vacuum atmosphere under an atmosphere of inert gas, 6,6-dibromoisoindole (Compound 3, 1.0 g, 2.93 mmol) and freshly dried potassium carbonate (2.43 g, 17.59 mmol) were added to a 100 ml three-necked flask. Anhydrous DMF (20 mL) followed by 1-bromo-2-ethylhexane (1.70 g, 8.79 mmol) was added to the resulting suspension. The mixture was heated to 100° C. and stirred for 15 hours then poured into water (500 mL). The organic phase was extracted with CH 2 Cl 2 , washed with brine, dried over MgSO 4 and the solvent was removed under reduced pressure. The dark red solid was purified by chromatography on silica. This was eluted with (CH2Cl2:hexane=2:3, volume ratio) to give 1.37 g of a brown solid (Compound 5) in a 90percent yield.
79% With potassium carbonate In N,N-dimethyl-formamide at 100℃; Inert atmosphere c) 7 g (16.6 mmol, 1 eq) of 2, 8 g (41.7mmol, 2.5 eq) of 1-bromo-2-ethylhexane and 13.9 g (100 mmol, 6 eq) of K2CO3 are stirred in DMF (200mL) under nitrogen overnight at 100° C. Then the mixture is poured in water and the solid filtrated and washed several times with water and ethanol. The solid is dissolved in a minimum of chloroform and precipitated in ethanol to yield 8.45 g of pure 4 as a red-violet powder.Yield 79percent;RMN 1H (CDCl3, δ ppm): 0.89 (m, 12H), 1.2-1.5 (m, 16H), 1.90 (m, 2H), 3.610 (m, 4H), 6.91 (d, 2H, J=1.76 Hz), 7.16 (dd, 2H, J=8.50, 1.76 Hz), 9.07 (d, 2H, J=8.50 Hz).
54.5%
Stage #1: With tetrabutylammomium bromide; potassium carbonate In N,N-dimethyl-formamide at 80℃; for 0.5 h; Inert atmosphere
Stage #2: Inert atmosphere
To a solution of 6,6'-dibromo-isoindigo (2.0 g, 4.76 mmol) in N,N-dimethyl formamide (DMF, 100 mL), tetrabutylammoniumbromide (0.1 g) and K2CO3 (3.95 g, 28.56 mmol) were added quickly under argon atmosphere. The mixture was stirred at 80 °C for 30 min, then the solution of 1-bromo-2-ethylhexane (2.30 g,11.90 mmol) in DMF (30 mL) was added. The mixture was stirred overnight. After cooling to room temperature, it was filtered, and the filtrate was extracted by CH2Cl2 and washed with brine. The organic layer was dried over anhydrous magnesium sulfate, andthen filtered. After removed the solvent by a rotary evaporator, the crude product was obtained, and it was further purified by column chromatography using petroleum ether/CH2Cl2 (3:1, v:v) as the eluent to yield a dark red solid (1.68 g, 54.5percent). 1H NMR (400 MHz,CDCl3, d/ppm):9.04 (d, J 8.5 Hz, 2H), 7.16 (dd, J1 1.4 Hz,J2 8.5 Hz, 2H), 6.90 (d, J 1.4 Hz, 2H), 3.63 (m, 4H), 1.84e1.81 (m,2H), 1.43e1.26 (m, 16H), 0.95e0.91 (m, 12H). 13C NMR (100 MHz,CDCl3, d/ppm): 168.07, 146.15, 132.55, 131.01, 126.69, 125.12, 120.36,111.54, 44.37, 37.43, 30.58, 28.58, 23.99, 23.08, 14.09, 10.66. FT-ICRMS (C32H40Br2N2O2) [M] m/z:calcd for 643.1529; found643.1530. Elemental anal. calcd. for (C32H40Br2N2O2): C, 59.64; H,6.26; N, 4.35. Found: C, 59.48; H, 6.34; N, 4.38.
Reference: [1] Patent: CN107739374, 2018, A, . Location in patent: Paragraph 0032; 0035; 0036
[2] Organic Letters, 2010, vol. 12, # 4, p. 660 - 663
[3] Macromolecules, 2010, vol. 43, # 20, p. 8348 - 8352
[4] Patent: US2010/297405, 2010, A1, . Location in patent: Page/Page column 20
[5] Dyes and Pigments, 2017, vol. 139, p. 403 - 411
[6] New Journal of Chemistry, 2013, vol. 37, # 2, p. 502 - 507
[7] Journal of Polymer Science, Part A: Polymer Chemistry, 2013, vol. 51, # 16, p. 3477 - 3485
[8] Chemistry Letters, 2014, vol. 43, # 12, p. 1870 - 1872
[9] RSC Advances, 2015, vol. 5, # 104, p. 85460 - 85469
  • 14
  • [ 18908-66-2 ]
  • [ 1210390-71-8 ]
  • [ 1210390-73-0 ]
  • [ 1210390-72-9 ]
  • [ 1147124-23-9 ]
Reference: [1] Organic Letters, 2010, vol. 12, # 4, p. 660 - 663
  • 15
  • [ 18908-66-2 ]
  • [ 389-58-2 ]
  • [ 365547-20-2 ]
YieldReaction ConditionsOperation in experiment
79% With sodium iodide; potassium hydroxide In dimethyl sulfoxide for 16 h; Inert atmosphere Example 5
Synthesis of 4,4-Bis-(2-ethyl-hexyl)-4H-cyclopenta[2,1-b;3,4-b']dithiophene
4H-Cyclopenta[2,1-b;3,4-b']dithiophene (1.5 g, 0.00843 mol) was dissolved in DMSO (50 mL).
After the solution was purged with nitrogen, and grounded KOH (1.89 g, 0.0337 mol), sodium iodide (50 mg), and 2-ethylhexyl bromide (3.25 g, 0.0169 mol) were sequentially added.
The reaction mixture was stirred overnight under nitrogen (c.a. 16 hours).
Water was added and the reaction was extracted with t-butylmethyl ether.
The organic layer was collected, dried over magnesium sulfate, and concentrated.
The residue was purified by chromatography using hexanes as eluent.
Fractions containing pure 4,4-Bis-(2-ethyl-hexyl)-4H-cyclopenta[2,1-b;3,4-b']dithiophene product were combined and concentrated.
The product was obtained as a colorless oil after drying under vacuum. Yield: 2.68 g (79percent).
1H NMR (CDCl3, 250 MHz): 7.13 (m, 2H), 6.94 (m, 2H), 1.88 (m, 4H), 0.94 (m, 16H), 0.78 (t, 6.4 Hz, 6H), 0.61 (t, 7.3 Hz, 6H).
2.61 g With potassium iodide; potassium hydroxide In dimethyl sulfoxide at 25℃; for 24 h; Inert atmosphere The gas in the flask to 200mL flask was replaced with argon, compound 1 (1.78g , 10.0mmol), 2- ethylhexyl bromide (5.83g, 25.0mmol), Potassium iodide (41.5mg, 0.25mmol), potassium hydroxide (1.68g, 30 . 0mmol) put, dissolved in dimethyl sulfoxide (35mL), room temperature (25°C ) In the mixture was stirred for 24 hours. After the reaction, water 100mL was added, and the product was extracted with hexane, silica gel column (developing solvent hexane) was purified by to give compound. 12 2.61 g.
2.61 g With potassium iodide; potassium hydroxide In dimethyl sulfoxide at 25℃; for 24 h; Inert atmosphere In the gas flask purged with argon200mL flask was added 1.78g (10.0mmol) compound 15,5.83g (25.0mmol) 2- ethylhexyl bromide, 41.5mg (0.25mmol) of potassium iodide, 1.68g (30.0mmol) of potassium hydroxide,Dissolved in dimethylsulfoxide 35mL was stirred at room temperature (25 ) 24 hours. 100mL of water was added to the reaction mixture, the product was extracted with hexane using hexane as a developing solvent was purified by silica gel column to obtain 2.61g compound 16.
2.61 g With potassium iodide; potassium hydroxide In dimethyl sulfoxide at 25℃; for 24 h; Inert atmosphere 200mL flask gas in the flask by argon-purged, was placed compound 15 (1.78g, 10.0mmol), 2- ethylhexyl bromide (5.83g, 25.0mmol), potassium iodide (41.5mg, 0.25mmol), potassium hydroxide (1.68g, 30.0mmol), which was dissolved in dimethyl sulfoxide (35mL), stirred at room temperature (25 ) 24 hours. After the reaction, water was added 100mL, the product was extracted with hexane, purified by silica gel column chromatography (developing solvent hexane) to give 2.61g of compound 16.

Reference: [1] Journal of Polymer Science, Part A: Polymer Chemistry, 2012, vol. 50, # 8, p. 1622 - 1635
[2] RSC Advances, 2014, vol. 4, # 71, p. 37738 - 37745
[3] RSC Advances, 2014, vol. 40, # 71, p. 37738 - 37745
[4] Macromolecules, 2010, vol. 43, # 2, p. 697 - 708
[5] Patent: US7772485, 2010, B2, . Location in patent: Page/Page column 11-12
[6] Chemistry - A European Journal, 2010, vol. 16, # 12, p. 3743 - 3752
[7] Macromolecules, 2010, vol. 43, # 3, p. 1253 - 1260
[8] Advanced Materials, 2018, vol. 30, # 6,
[9] Journal of the American Chemical Society, 2012, vol. 134, # 1, p. 539 - 547
[10] Journal of Polymer Science, Part A: Polymer Chemistry, 2010, vol. 48, # 6, p. 1423 - 1432
[11] Journal of Materials Chemistry, 2011, vol. 21, # 11, p. 3895 - 3902
[12] Patent: JP2015/180621, 2015, A, . Location in patent: Paragraph 0232
[13] Patent: CN105439976, 2016, A, . Location in patent: Paragraph 0234; 0235
[14] Patent: CN105601662, 2016, A, . Location in patent: Paragraph 0528; 0529; 0530; 0531; 0532
[15] Journal of Materials Chemistry C, 2018, vol. 6, # 39, p. 10532 - 10537
  • 16
  • [ 18908-66-2 ]
  • [ 389-58-2 ]
  • [ 365547-20-2 ]
Reference: [1] Journal of Polymer Science, Part A: Polymer Chemistry, 2013, vol. 51, # 22, p. 4912 - 4922
  • 17
  • [ 18908-66-2 ]
  • [ 1226782-13-3 ]
Reference: [1] Patent: US8933441, 2015, B2,
[2] Patent: CN105968125, 2016, A,
[3] Patent: CN105968124, 2016, A,
[4] Patent: KR2018/38433, 2018, A,
  • 18
  • [ 18908-66-2 ]
  • [ 1392422-47-7 ]
Reference: [1] Journal of Polymer Science, Part A: Polymer Chemistry, 2014, vol. 52, # 16, p. 2356 - 2366
[2] Journal of Materials Chemistry A, 2018, vol. 6, # 42, p. 20904 - 20915
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