67665-45-6

Basic information

• Product Name: 9,9'-Spirobi[9H-fluorene]-2,2'-diamine
• Synonyms: 9,9'-Spirobi[9H-fluorene], 2,2'-aMino-;9,9'-Spirobi[fluorene]-2,2'-diaMine;9,9'-Spirobi[9H-fluorene]-2,2'-diamine 20g;9,9'-Spirobi[9H-fluorene]-2,2'-diamine;9,9'-Spriobifluorene-2,2'-diamine
• CAS NO: 67665-45-6
• Molecular Formula: C₂₅H₁₈N₂
• Molecular Weight: 346.42
• Mol File: 67665-45-6.mol
• Article Data: 2

Chemical Properties

• Appearance: /
• Density: 1.36
• Storage Temp.: Keep in dark place,Inert atmosphere,Room temperature
• CAS DataBase Reference: 9,9'-Spirobi[9H-fluorene]-2,2'-diamine(CAS DataBase Reference)
• NIST Chemistry Reference: 9,9'-Spirobi[9H-fluorene]-2,2'-diamine(67665-45-6)
• EPA Substance Registry System: 9,9'-Spirobi[9H-fluorene]-2,2'-diamine(67665-45-6)

Safety Data

• Hazardous Substances Data: 67665-45-6(Hazardous Substances Data)

Usage

General Description

9,9'-Spirobi[9H-fluorene]-2,2'-diamine is an organic compound with the chemical formula C26H18N2. Its systematic name is 2,2'-(9,9'-spirobifluorene-2,2'-diyl)dianiline. It belongs to a class of chemicals known as Polycyclic Aromatic Hydrocarbons, which contain fused aromatic rings. 9,9'-Spirobi[9H-fluorene]-2,2'-diamine has been utilized in organic chemistry as a chemical building block. Its specific properties, such as melting point, boiling point, and solubility, will be determined by its preparation and purification.

Synthetic route

(rac)-2,2'-dinitro-9,9'-spirobifluorene (67665-46-7) → 2,2′-diamino-9,9′-spirobifluorene (67665-45-6)

Conditions	Yield
With sodium tetrahydroborate; palladium on activated charcoal In methanol at 20℃; for 12h;	76%
With hydrogenchloride; iron

2,2′-dibromo-9,9′-spirobi[9H-fluorene] (67665-47-8) → 2,2′-diamino-9,9′-spirobifluorene (67665-45-6)

Conditions	Yield
With lithium hexamethyldisilazane; CyJohnPhos; tris-(dibenzylideneacetone)dipalladium(0) In tetrahydrofuran at 65℃; for 15h;	45%

ammonium hydroxide (1336-21-6) + dinitrospirobifluorene + 9,9'-spirobifluorene (159-66-0) + iron (7439-89-6) + Rochelle's salt (304-59-6) → 2,2′-diamino-9,9′-spirobifluorene (67665-45-6)

Conditions	Yield
With concentrated aqueous HNO3 In ethanol; water; pyrographite; acetic acid

2,2′-diamino-9,9′-spirobifluorene (67665-45-6) → 3,3'-dibromo-9,9'-spirobifluorene-2,2'-diamine

Conditions	Yield
With N-Bromosuccinimide In dichloromethane for 1.5h;	89.2%

2,2′-diamino-9,9′-spirobifluorene (67665-45-6) → (rac)-2,2'-diiodo-9,9'-spirobifluorene (790674-48-5)

Conditions	Yield
Stage #1: 2,2′-diamino-9,9′-spirobifluorene With hydrogenchloride; sodium nitrite In water at 0℃; for 0.75h; Stage #2: With potassium iodide In water for 16h; Sandmeyer reaction;	72%

4-tolyl iodide (624-31-7) + 2,2′-diamino-9,9′-spirobifluorene (67665-45-6) → 2,2'-bis(ditolylamino)-9,9'-spirobifluorene

Conditions	Yield
With sodium t-butanolate; palladium diacetate; tri-tert-butyl phosphine In toluene Heating / reflux;	72%

iodobenzene (591-50-4) + 2,2′-diamino-9,9′-spirobifluorene (67665-45-6) → 2,2’-bis(N,N-diphenylamine)-9,9'-spirobifluorene

Conditions	Yield
With sodium t-butanolate; palladium diacetate; tri-tert-butyl phosphine In toluene Heating / reflux;	70%

1-bromo-4-tert-butylbenzene (3972-65-4) + 2,2′-diamino-9,9′-spirobifluorene (67665-45-6) → 2,2'-bis[di-(4-t-butylphenyl)amino]-9,9'-spirobifluorene

Conditions	Yield
With sodium t-butanolate; palladium diacetate; tri-tert-butyl phosphine In toluene for 48h; Heating / reflux;	60%

2,2′-diamino-9,9′-spirobifluorene (67665-45-6) → 2,2′-dibromo-9,9′-spirobi[9H-fluorene] (67665-47-8)

Conditions	Yield
With tert.-butylnitrite; copper(ll) bromide In acetonitrile at 60℃; for 0.5h;	58%

N-butyl-1,7-di(4-tert-butyl)phenoxylperylene-3,4-dicarboxylic imide-9,10-dicarboxylic anhydride (1055917-19-5) + 2,2′-diamino-9,9′-spirobifluorene (67665-45-6) → C73H57N3O6 (1380497-15-3)

Conditions	Yield
With 1H-imidazole In toluene for 5h; Reflux; Inert atmosphere;	37%

2,2′-diamino-9,9′-spirobifluorene (67665-45-6) + 5-[1-hydroxy-meth-(E)-ylidene]-2,2,4,4-tetramethyl cyclopentanone → C45H42N2

Conditions	Yield
Stage #1: 2,2′-diamino-9,9′-spirobifluorene; 5-[1-hydroxy-meth-(E)-ylidene]-2,2,4,4-tetramethyl cyclopentanone In toluene at 160℃; for 10h; Stage #2: With polyphosphoric acid In toluene at 160℃; for 16h; Inert atmosphere;	29%

2,2′-diamino-9,9′-spirobifluorene (67665-45-6) + N,N-Dimethylcarbamoyl chloride (79-44-7) → N',N',N''',N'''-tetramethyl-N,N''-[9,9']spirobifluorene-2,2'-diyl-di-urea

Conditions	Yield
With pyridine; diethyl ether; benzene

2,2′-diamino-9,9′-spirobifluorene (67665-45-6) + 6-tert-butyl-8-(5,7-di-tert-butyl-benzooxazol-2-ylamino)-4-oxo-4H-chromene-2-carboxylic acid 2,5-dioxo-pyrrolidin-1-yl ester → C83H82N6O8

Conditions	Yield
In tetrahydrofuran Yield given;

(R)-2,3-bis-tert-butoxycarbonylaminopropionic acid (159652-30-9) + 2,2′-diamino-9,9′-spirobifluorene (67665-45-6) → C51H62N6O10 + C38H40N4O5

Conditions	Yield
With benzotriazol-1-ol; N-(3-dimethylaminopropyl)-N-ethylcarbodiimide In dichloromethane at 20℃; for 48h; Inert atmosphere;	A 67.8 mg B 25.8 mg

2,2′-diamino-9,9′-spirobifluorene (67665-45-6) → C63H54N6O6

Conditions	Yield
Multi-step reaction with 3 steps 1: benzotriazol-1-ol; N-(3-dimethylaminopropyl)-N-ethylcarbodiimide / dichloromethane / 48 h / 20 °C / Inert atmosphere 2: trifluoroacetic acid / 20 °C / Inert atmosphere 3: dimethyl sulfoxide / 50 °C View Scheme

2,2′-diamino-9,9′-spirobifluorene (67665-45-6) → C31H30N6O2

Conditions	Yield
Multi-step reaction with 2 steps 1: benzotriazol-1-ol; N-(3-dimethylaminopropyl)-N-ethylcarbodiimide / dichloromethane / 48 h / 20 °C / Inert atmosphere 2: trifluoroacetic acid / 20 °C / Inert atmosphere View Scheme

2,2-di-(4-methoxyphenyl)acetaldehyde (5032-08-6) + 2,2′-diamino-9,9′-spirobifluorene (67665-45-6) → C89H74N2O8

Conditions	Yield
Dean-Stark; Reflux;

Upstream product

• 67665-46-7 (rac)-2,2'-dinitro-9,9'-spirobifluorene 
• 67665-47-8 2,2′-dibromo-9,9′-spirobi[9H-fluorene] 
• 1336-21-6 ammonium hydroxide 
• 159-66-0 9,9'-spirobifluorene 
• 7439-89-6 iron 
• 304-59-6 Rochelle's salt 

Downstream Products

• 1380497-15-3 C₇₃H₅₇N₃O₆ 
• 67665-47-8 2,2′-dibromo-9,9′-spirobi[9H-fluorene] 

Relevant articles and documents

Synthesis of enantiomerically pure dissymmetric 2,2′-disubstituted 9,9′-spirobifluorenes

Racemic dissymmetric 2,2′-dihydroxy-9,9′-spirobifluorene was prepared and resolved by clathrate formation with (R,R)-(+)-2,3-dimethoxy-N,N, N′,N′-tetracyclohexylsuccindiamide, giving rise to both enantiomers in very good yields. The absolute stereochemistry of the resolved material could be assigned by an X-ray structure analysis of single crystals of the clathrate. Enantiomerically pure diols could be transformed into the corresponding ditriflates, which were then used as starting materials in different cross-coupling procedures to provide a number of new enantiomerically pure spiro compounds bearing versatile functional groups suitable for further elaboration, as demonstrated by some examples. Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005.