67665-45-6

Usage

Uses

Used in Organic Chemistry:
9,9'-Spirobi[9H-fluorene]-2,2'-diamine is used as a chemical building block for the synthesis of various organic compounds. Its unique structure and properties make it a valuable intermediate in the creation of complex molecules and materials.
Used in Pharmaceutical Industry:
9,9'-Spirobi[9H-fluorene]-2,2'-diamine is used as a precursor in the development of pharmaceutical compounds. Its ability to form stable bonds with other molecules allows for the creation of new drug candidates with potential therapeutic applications.
Used in Material Science:
9,9'-Spirobi[9H-fluorene]-2,2'-diamine is used as a component in the development of advanced materials. Its incorporation into polymers and other materials can enhance their properties, such as stability, conductivity, and optical characteristics, making them suitable for various applications in the material science field.
Used in Research and Development:
9,9'-Spirobi[9H-fluorene]-2,2'-diamine is used as a research tool in the study of chemical reactions and processes. Its reactivity and interaction with other compounds provide valuable insights into the mechanisms of organic chemistry and can lead to the discovery of new synthetic pathways and methodologies.

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 academic research and scientific papers

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.

USE OF SPIRO COMPOUNDS AS LASER DYES

Use of spiro compounds of formula (I), where K and K are, independently of one another, conjugated systems, as a laser dye.