286438-45-7

Basic information

• Product Name: 9 9-DIDODECYL-2 7-DIBROMOFLUORENE 97
• Synonyms: 2,7-Dibromo-9,9-di(1-dodecyl)-9H-fluorene;9,9-Di-n-dodecyl-2,7-dibroMofluorene, 98%;2,7-DibroMo-9,9-didodecylfluorene,9,9-didodecyl-2,7-dibroMofluorene;2,7-DibroMo-9,9-didodecyl-9H-fluorene;9H-Fluorene,2,7-dibromo-9,9-didodecyl-;9 9-DIDODECYL-2 7-DIBROMOFLUORENE 97;9,9-DIDODECYL-2,7-DIBROMOFLUORENE,99%;2,7-Dibromo-9,9-didodecylfluorene (This product is only available in Japan.)
• CAS NO: 286438-45-7
• Molecular Formula: C₃₇H₅₆Br₂
• Molecular Weight: 660.65
• Product Categories: Fluorene Derivatives;Organic Electronics and Photonics;Polyfluorene (PFO, PFE) Monomers;Synthetic Tools and Reagents;Fluorene Series
• Mol File: 286438-45-7.mol
• Article Data: 15

Chemical Properties

• Melting Point: 50-55 °C(lit.)
• Boiling Point: 180 °C0.15 mm Hg(lit.)
• Flash Point: >230 °F
• Appearance: /
• Density: 1.13 g/cm³
• Vapor Pressure: 3.92E-16mmHg at 25°C
• Refractive Index: 1.529
• Storage Temp.: Sealed in dry,Room Temperature
• CAS DataBase Reference: 9 9-DIDODECYL-2 7-DIBROMOFLUORENE 97(CAS DataBase Reference)
• NIST Chemistry Reference: 9 9-DIDODECYL-2 7-DIBROMOFLUORENE 97(286438-45-7)
• EPA Substance Registry System: 9 9-DIDODECYL-2 7-DIBROMOFLUORENE 97(286438-45-7)

Safety Data

• Safety Statements: 22-24/25
• WGK Germany: 3
• Hazardous Substances Data: 286438-45-7(Hazardous Substances Data)

Usage

Chemical Properties

light yellow powder

Uses

It is an intermediate for polymeric light-emitting diodes.

InChI:InChI=1/C37H56Br2/c1-3-5-7-9-11-13-15-17-19-21-27-37(28-22-20-18-16-14-12-10-8-6-4-2)35-29-31(38)23-25-33(35)34-26-24-32(39)30-36(34)37/h23-26,29-30H,3-22,27-28H2,1-2H3

Synthetic route

2,7-dibromo-9H-fluorene (16433-88-8) + 1-dodecylbromide (143-15-7) → 2,7-dibromo-9,9-di-n-dodecylfluorene (286438-45-7)

Conditions	Yield
With potassium tert-butylate In tetrahydrofuran at 0 - 20℃; for 12h;	92%
With tetrabutylammomium bromide; water; sodium hydroxide In dimethyl sulfoxide at 20℃; for 3h;	87%
With tetrabutylammomium bromide; sodium hydroxide In water; toluene at 80℃; for 24h; Inert atmosphere;	86.6%

9,9-didodecyl-9H-fluorene (123864-03-9) → 2,7-dibromo-9,9-di-n-dodecylfluorene (286438-45-7)

Conditions	Yield
With bromine; iodine In dichloromethane at 20℃; for 20h;	80%

9H-fluorene (86-73-7) → 2,7-dibromo-9,9-di-n-dodecylfluorene (286438-45-7)

Conditions	Yield
Multi-step reaction with 2 steps 1.1: n-BuLi / hexane; tetrahydrofuran / 1.5 h / -60 °C 1.2: 80 percent / tetrahydrofuran; hexane / 0.5 h / -60 °C 2.1: 80 percent / bromine / I2 / CH2Cl2 / 20 h / 20 °C View Scheme
Multi-step reaction with 2 steps 1: bromine; iodine / dichloromethane / 15 h / 20 °C 2: potassium tert-butylate / tetrahydrofuran / 12 h / 0 - 20 °C View Scheme
Multi-step reaction with 2 steps 1.1: acetic acid; N-Bromosuccinimide; hydrogen bromide / 3 h / 20 °C 2.1: potassium hydroxide / toluene / 1 h / Inert atmosphere 2.2: 12 h / 60 °C / Inert atmosphere View Scheme
Multi-step reaction with 2 steps 1: bromine / chloroform / 10 h / 0 °C / Darkness 2: sodium hydroxide; tetrabutylammomium bromide / toluene; water / 24 h / 80 °C / Inert atmosphere View Scheme

1-dodecylbromide (143-15-7) → 2,7-dibromo-9,9-di-n-dodecylfluorene (286438-45-7)

Conditions	Yield
Multi-step reaction with 2 steps 1.1: n-BuLi / hexane; tetrahydrofuran / 1.5 h / -60 °C 1.2: 80 percent / tetrahydrofuran; hexane / 0.5 h / -60 °C 2.1: 80 percent / bromine / I2 / CH2Cl2 / 20 h / 20 °C View Scheme

2,7-dibromo-9,9-di-n-dodecylfluorene (286438-45-7) + trimethyltin(IV)chloride (1066-45-1) → 2,7-bis(trimethylstannyl)-9,9-didodecylfluorene

Conditions	Yield
Stage #1: 2,7-dibromo-9,9-di-n-dodecylfluorene With n-butyllithium In tetrahydrofuran; hexane at -78℃; for 1h; Stage #2: trimethyltin(IV)chloride In tetrahydrofuran; hexane at -78 - 20℃; for 12h;	96%

2,7-dibromo-9,9-di-n-dodecylfluorene (286438-45-7) + 2-Isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (61676-62-8) → 2,2'-(9,9-didodecyl-9H-fluorene-2,7-diyl)bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolane) (749900-93-4)

Conditions	Yield
Stage #1: 2,7-dibromo-9,9-di-n-dodecylfluorene With tert.-butyl lithium In tetrahydrofuran; pentane at -78℃; for 1h; Inert atmosphere; Stage #2: 2-Isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane In tetrahydrofuran; pentane at -78 - 20℃; Inert atmosphere;	90%
With tert.-butyl lithium In not given 1) t-BuLi, -78°C; 2.) dioxaborolane;	90%
Stage #1: 2,7-dibromo-9,9-di-n-dodecylfluorene With tert.-butyl lithium In tetrahydrofuran; pentane at -78℃; for 0.5h; Inert atmosphere; Stage #2: 2-Isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane In tetrahydrofuran; pentane at -78 - 20℃; Inert atmosphere;	90%

2,7-dibromo-9,9-di-n-dodecylfluorene (286438-45-7) + trimethylsilylacetylene (1066-54-2) → ((9,9-didodecylfluorene-2,7-diyl)bis(ethyne-2,1-diyl))bis(trimethylsilane) (1427465-81-3)

Conditions	Yield
With bis-triphenylphosphine-palladium(II) chloride; copper(l) iodide at 20 - 70℃; for 12.5h; Sonogashira Cross-Coupling; Alkaline conditions;	89%
With bis-triphenylphosphine-palladium(II) chloride; copper(l) iodide; triethylamine at 70℃; for 12h;	89%
With bis-triphenylphosphine-palladium(II) chloride; copper(l) iodide at 20 - 75℃; Sonogashira Cross-Coupling; Inert atmosphere;	73%
Stage #1: 2,7-dibromo-9,9-di-n-dodecylfluorene With bis-triphenylphosphine-palladium(II) chloride; copper(l) iodide; triethylamine; triphenylphosphine In tetrahydrofuran for 0.1h; Sonogashira Cross-Coupling; Inert atmosphere; Glovebox; Sealed tube; Stage #2: trimethylsilylacetylene In tetrahydrofuran at 70℃; Sonogashira Cross-Coupling; Inert atmosphere; Sealed tube; Glovebox;	54.5%
With bis-triphenylphosphine-palladium(II) chloride; copper(l) iodide; N-ethyl-N,N-diisopropylamine at 75℃; for 20h; Sonogashira Cross-Coupling; Inert atmosphere; Schlenk technique;

2,7-dibromo-9,9-di-n-dodecylfluorene (286438-45-7) + N,N-dimethyl-formamide (68-12-2, 33513-42-7) → 9,9-didodecyl-9H-fluorene-2,7-dicarbaldehyde (1450727-06-6)

Conditions	Yield
Stage #1: 2,7-dibromo-9,9-di-n-dodecylfluorene With n-butyllithium In diethyl ether at -78℃; for 0.5h; Stage #2: N,N-dimethyl-formamide In diethyl ether at -78 - 20℃;	88%

2,7-dibromo-9,9-di-n-dodecylfluorene (286438-45-7) + bis(pinacol)diborane (73183-34-3) → 2,2'-(9,9-didodecyl-9H-fluorene-2,7-diyl)bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolane) (749900-93-4)

Conditions	Yield
With (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride In N,N-dimethyl-formamide at 90℃; for 12h;	87%
With (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; potassium acetate In 1,4-dioxane at 80℃; Miyaura reaction; Inert atmosphere;	76%
Stage #1: 2,7-dibromo-9,9-di-n-dodecylfluorene; bis(pinacol)diborane With potassium acetate In 1,4-dioxane; dimethyl sulfoxide for 1h; Inert atmosphere; Stage #2: With palladium bis[bis(diphenylphosphino)ferrocene] dichloride In 1,4-dioxane; dimethyl sulfoxide at 80℃; for 12h; Inert atmosphere;	74%

2,7-dibromo-9,9-di-n-dodecylfluorene (286438-45-7) + 2-methyl-but-3-yn-2-ol (115-19-5) → 4,4'-(9,9-didodecyl-9H-fluorene-2,7-diyl)bis(2-methylbut-3-yn-2-ol) (1275593-74-2)

Conditions	Yield
With copper(l) iodide; tetrakis(triphenylphosphine) palladium(0); triethylamine In tetrahydrofuran at 60℃; for 20h; Sonogashira coupling; Inert atmosphere;	87%
With bis-triphenylphosphine-palladium(II) chloride; copper(l) iodide; triethylamine; triphenylphosphine In tetrahydrofuran for 10h; Reflux; Inert atmosphere;	42.8%

2,7-dibromo-9,9-di-n-dodecylfluorene (286438-45-7) + 9H-carbazole (86-74-8) → 2,7-bis(carbazol-N-yl)-9,9-didodecylfluorene

Conditions	Yield
With potassium phosphate; copper(l) iodide; trans-1,2-Diaminocyclohexane In toluene for 24h; Ullmann Condensation; Inert atmosphere; Reflux;	87%

2,7-dibromo-9,9-di-n-dodecylfluorene (286438-45-7)

Conditions	Yield
With n-butyllithium; N,N,N,N,-tetramethylethylenediamine In diethyl ether; hexane at -78 - 20℃;	85%

2,7-dibromo-9,9-di-n-dodecylfluorene (286438-45-7) + 3,6-di(N-carbazolyl)carbazole (606129-90-2) → C73H78BrN3

Conditions	Yield
With potassium phosphate; copper(l) iodide; trans-1,2-cyclohexanediamine In toluene for 24h; Ullmann Condensation; Reflux; Inert atmosphere;	76%

2,7-dibromo-9,9-di-n-dodecylfluorene (286438-45-7) + 3,6-bis(3,6-di-tert-butylcarbazol-N-yl)carbazole (551951-04-3) → 2-bromo-7-[3,6-bis(3,6-di(tert-butyl)-9H-carbazol-9-yl)-9H-carbazol-9-yl]-9,9-didodecyl-9H-fluorene

Conditions	Yield
With potassium phosphate; copper(l) iodide; trans-1,2-Diaminocyclohexane In toluene for 24h; Ullmann Condensation; Inert atmosphere; Reflux;	76%

2,7-dibromo-9,9-di-n-dodecylfluorene (286438-45-7) + 9H-carbazole (86-74-8) → 2-bromo-7-(carbazol-N-yl)-9,9-didodecylfluorene

Conditions	Yield
With potassium phosphate; copper(l) iodide; trans-1,2-Diaminocyclohexane In toluene for 24h; Ullmann Condensation; Inert atmosphere; Reflux;	75%
With potassium phosphate; copper(l) iodide; trans-1,2-cyclohexanediamine In toluene for 24h; Ullmann Condensation; Reflux; Inert atmosphere;	73%

2,7-dibromo-9,9-di-n-dodecylfluorene (286438-45-7) → 2,7-dibromo-9,9-didodecyl-1,6-dinitrofluorene

Conditions	Yield
With ammonium cerium (IV) nitrate; sulfuric acid In dichloromethane at 0℃; for 1h;	74.56%

2,7-dibromo-9,9-di-n-dodecylfluorene (286438-45-7) + 3,6-di(tert-butyl)-9H-carbazole (37500-95-1) → 2-bromo-7-[3,6-di(tert-butyl)-9H-carbazol-9-yl]-9,9-didodecyl-9H-fluorene

Conditions	Yield
With potassium phosphate; copper(l) iodide; trans-1,2-Diaminocyclohexane In toluene for 24h; Ullmann Condensation; Inert atmosphere; Reflux;	73%

2,7-dibromo-9,9-di-n-dodecylfluorene (286438-45-7) + copper(I) cyanide → 9,9-didodecyl-2,7-dicyanofluorene (388602-19-5)

Conditions	Yield
In N,N-dimethyl-formamide for 24h; Heating;	70%

2,7-dibromo-9,9-di-n-dodecylfluorene (286438-45-7) + 3,6-di{3,6-di(9H-carbazol-9-yl)-9H-carbazol-9-yl}-9H-carbazole (1122624-11-6) → C121H106BrN7

Conditions	Yield
With potassium phosphate; copper(l) iodide; trans-1,2-cyclohexanediamine In toluene for 24h; Ullmann Condensation; Reflux; Inert atmosphere;	70%

2,7-dibromo-9,9-di-n-dodecylfluorene (286438-45-7) + 3,6-bis[3,6-bis(3,6-di-tert-butylcarbazol-N-yl)carbazol-N-yl]carbazole (1068116-44-8) → 2-bromo-7-{3,6-bis[3,6-bis(3,6-di(tert-butyl)-9H-carbazol-9-yl)-9H-carbazol-9-yl]-9H-carbazol-9-yl}-9,9-didodecyl-9H-fluorene (1618678-86-6)

Conditions	Yield
With potassium phosphate; copper(l) iodide; trans-1,2-Diaminocyclohexane In toluene for 24h; Ullmann Condensation; Inert atmosphere; Reflux;	70%

2,7-dibromo-9,9-di-n-dodecylfluorene (286438-45-7) + pinacol vinylboronate (75927-49-0) → 2,7-bis(4',4',5',5',-tetramethyl-2'-vinyl-1',3',2'-dioxaborate)-9,9-bis(2-dodecyl)fluorene

Conditions	Yield
With palladium diacetate; triethylamine; tris-(o-tolyl)phosphine In N,N-dimethyl-formamide at 110℃; for 7h; Inert atmosphere;	69%

2,7-dibromo-9,9-di-n-dodecylfluorene (286438-45-7) + 4-ethenyl-4'-methyl-1,2-stilbene → C54H71Br

Conditions	Yield
With palladium diacetate; triethylamine; triphenylphosphine In N,N-dimethyl-formamide at 110℃; for 48h; Heck Reaction; Inert atmosphere;	54%

2,7-dibromo-9,9-di-n-dodecylfluorene (286438-45-7) → 2,7-diazido-9,9-didodecane-fluorene (866889-88-5)

Conditions	Yield
With 4-toluenesulfonyl azide; tert.-butyl lithium In tetrahydrofuran; pentane at -78℃;	53%
With n-butyllithium; 4-toluenesulfonyl azide In tetrahydrofuran Inert atmosphere;	8%
Multi-step reaction with 2 steps 1: (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride / 1,4-dioxane / 80 °C / Inert atmosphere; Schlenk technique 2: sodium azide; copper(l) iodide / methanol / 8 h / 55 °C View Scheme

2,7-dibromo-9,9-di-n-dodecylfluorene (286438-45-7) + acetyl chloride (75-36-5) → 9,9-didodecyl-2,7-bis(acetylthio)fluorene (1586808-77-6)

Conditions	Yield
Stage #1: 2,7-dibromo-9,9-di-n-dodecylfluorene With sodium thiomethoxide at 120℃; for 18h; Inert atmosphere; Stage #2: acetyl chloride at 20℃; for 3h; Inert atmosphere;	48%

2,7-dibromo-9,9-di-n-dodecylfluorene (286438-45-7) + thianthren-1-yl boronic acid (108847-76-3) → 2,7-bis(1-thianthrene)-9,9-didodecylfluorene (1373485-23-4)

Conditions	Yield
With tetrakis(triphenylphosphine) palladium(0); potassium carbonate In water; toluene at 90℃; for 24h; Suzuki Coupling; Inert atmosphere;	47%

2,7-dibromo-9,9-di-n-dodecylfluorene (286438-45-7) + carbon dioxide (124-38-9) + 2-Isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (61676-62-8) → C44H69BO4 (1269505-28-3)

Conditions	Yield
Stage #1: 2,7-dibromo-9,9-di-n-dodecylfluorene With n-butyllithium In tetrahydrofuran at -78℃; for 0.916667h; Inert atmosphere; Stage #2: 2-Isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane In tetrahydrofuran at -78 - -50℃; for 1.08333h; Stage #3: carbon dioxide Further stages;	36%

2,7-dibromo-9,9-di-n-dodecylfluorene (286438-45-7) + C44H69BO4 (1269505-28-3) → C113H170O4 (1269505-29-4)

Conditions	Yield
With tetrakis(triphenylphosphine) palladium(0); tetrabutylammomium bromide; potassium carbonate In tetrahydrofuran; water at 90℃; for 12h; Suzuki coupling; Inert atmosphere;	33%

2,7-dibromo-9,9-di-n-dodecylfluorene (286438-45-7) + C26H42BNO4S (1610851-65-4) → C77H116N2O4S2 (1610851-62-1)

Conditions	Yield
With potassium phosphate; tris-(dibenzylideneacetone)dipalladium(0); XPhos In 1,2-dimethoxyethane at 120℃; for 16h; Suzuki-Miyaura Coupling; Schlenk technique; Inert atmosphere; Glovebox;	32%

2,7-dibromo-9,9-di-n-dodecylfluorene (286438-45-7) + 4-bromobenzenemethanol (873-75-6) → polymer, Mn: 4000 g/mol, PDI: 1.5; monomer(s): 2,7-dibromo-9,9-di-n-dodecylfluorene; 4-bromobenzyl alcohol

Conditions	Yield
With bis(1,5-cyclooctadiene)nickel (0); 1,5-cis,cis-cyclooctadiene; 1,1'-bipyridyl In pentane at 85℃; for 48h;

2,7-dibromo-9,9-di-n-dodecylfluorene (286438-45-7) → 9,9-didodecylfluorene-2,7-dicarboxylic acid dichloride (388602-21-9)

Conditions	Yield
Multi-step reaction with 3 steps 1: 70 percent / dimethylformamide / 24 h / Heating 2: 75 percent / phosphoric acid; H2O / 24 h / 170 °C 3: 81 percent / thionyl chloride / DMF / 13 h / 20 - 50 °C View Scheme

2,7-dibromo-9,9-di-n-dodecylfluorene (286438-45-7) → 9,9-didodecyl-2,7-bis(pyrrol-2-yl)fluorene

Conditions	Yield
Multi-step reaction with 6 steps 1: 70 percent / dimethylformamide / 24 h / Heating 2: 75 percent / phosphoric acid; H2O / 24 h / 170 °C 3: 81 percent / thionyl chloride / DMF / 13 h / 20 - 50 °C 4: 80 percent / triethylamine / benzene / 7 h / 20 - 50 °C 5: phosgene / DMF / toluene / 13 h / 20 - 40 °C 6: potassium tert-butoxide / tetrahydrofuran / 1 h / -10 - 0 °C View Scheme

2,7-dibromo-9,9-di-n-dodecylfluorene (286438-45-7) → 9,9-didodecylfluorene-2,7-dicarboxylic acid diallylamide (388602-22-0)

Conditions	Yield
Multi-step reaction with 4 steps 1: 70 percent / dimethylformamide / 24 h / Heating 2: 75 percent / phosphoric acid; H2O / 24 h / 170 °C 3: 81 percent / thionyl chloride / DMF / 13 h / 20 - 50 °C 4: 80 percent / triethylamine / benzene / 7 h / 20 - 50 °C View Scheme

Upstream product

• 16433-88-8 2,7-dibromo-9H-fluorene 
• 143-15-7 1-dodecylbromide 
• 86-73-7 9H-fluorene 
• 123864-03-9 9,9-didodecyl-9H-fluorene 

Downstream Products

• 749900-93-4 2,2'-(9,9-didodecyl-9H-fluorene-2,7-diyl)bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolane) 
• 1450727-06-6 9,9-didodecylfluorene-2,7-dicarbaldehyde 
• 1586808-78-7 9,9-didodecyl-2,7-bis((4-(acetylthio)phenyl)ethynyl)fluorene 

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The invention discloses a preparation method of 2,7-dibromo-9,9-dialkyl-1,6-binitro-fluorene and belongs to the field of organic chemical synthesis. The preparation method comprises the following steps: utilizing fluorene as a raw material and reacting with liquid bromine to obtain 2,7-dibromo-fluorene; then, dissolving the 2,7-dibromo-fluorene into a methylbenzene and NaOH water solution and reacting with hylogenated hydrocarbon to obtain 2,7-dibromo-9,9-dialkyl-fluorene; then, reacting the 2,7-dibromo-9,9-dialkyl-fluorene with ceric ammonium nitrate to obtain a final product of 2,7-dibromo-9,9-dialkyl-1,6-binitro-fluorene. By means of utilizing the ceric ammonium nitrate as a nitration reagent, the preparation method disclosed by the invention has the advantages of quick reaction speed,good selectivity, moderate reaction condition and small byproduct. Furthermore, two nitro groups are introduced into 1,6 sites of the flurene for the first time, so that obtained asymmetric binitro-fluorene can be applied to design synthesis of organic photoelectric materials.

New heterobimetallic Au(i)-Pt(ii) polyynes achieving a good trade-off between transparency and optical power limiting performance

Two series of new heterobimetallic Au(i)-Pt(ii) polyynes have been easily synthesized by cross-coupling under mild conditions. The absorption profiles of these two series of Au(i)-Pt(ii) polyynes are quite similar. However, the Au(i)-Pt(ii) polyynes with a 1,4-bis(diphenylphosphino)benzene ligand show stronger triplet (T1) emission and superior optical power limiting (OPL) performance than the corresponding Au(i)-Pt(ii) polyynes with a 1,3-bis(diphenylphosphino)propane ligand. Hence, the 1,4-bis(diphenylphosphino)benzene ligand is more effective than the 1,3-bis(diphenylphosphino)propane ligand for optimizing the transparency and OPL ability of OPL materials. When compared with the corresponding homometallic Pt(ii) polyynes, these heterobimetallic Au(i)-Pt(ii) polyynes display a blue shift in their absorption spectra, showing better transparency in the visible-light region. Besides, these heterobimetallic Au(i)-Pt(ii) polyynes show stronger OPL ability than their corresponding homometallic Pt(ii) polyynes as well as the state-of-the-art OPL material C60, demonstrating their enormous application potential in the nonlinear optics field. In brief, the introduction of Au(i) precursors with tetrahedral diphosphine ligands into the backbone of Pt(ii) polyynes can simultaneously achieve enhanced transparency and high OPL ability for OPL materials, providing a new strategy to optimize OPL materials.