68654-22-8

Basic information

• Product Name: syn-(Methyl,methyl)bimane
• Synonyms: syn-(Methyl,methyl)bimane;2,3,5,6-Tetramethyl-pyrazolo[1,2-a]pyrazole-1,7-dione;2,3,7,8-Tetramethyl-1,5-diaza-bicyclo(3.3.0)octa-2,7-dien-4,6-dione;3,4,6,7-Tetramethyl-1,5-diazabicyclo[3.3.0]octa-3,6-diene-2,8-dione;3,4,6,7-Tetramethyl-1,5-diazabicyclo[3.3.0]octa-3,6-diene-2,8-dione;2,3,5,6-Tetramethyl-pyrazolo[1,2-α]pyrazole-1,7-dione;methylbimane
• CAS NO: 68654-22-8
• Molecular Formula: C₁₀H₁₂N₂O₂
• Molecular Weight: 192.217
• Product Categories: Heterocyclic Compounds;Heterocycles
• Mol File: 68654-22-8.mol

Chemical Properties

• Melting Point: 211-2120C
• Boiling Point: 280.817°C at 760 mmHg
• Flash Point: 116.704°C
• Appearance: /
• Density: 1.282g/cm³
• Vapor Pressure: 0.004mmHg at 25°C
• Refractive Index: 1.598
• Storage Temp.: Refrigerator
• Solubility: Chloroform (Slightly, Heated), Methanol (Slightly)
• CAS DataBase Reference: syn-(Methyl,methyl)bimane(CAS DataBase Reference)
• NIST Chemistry Reference: syn-(Methyl,methyl)bimane(68654-22-8)
• EPA Substance Registry System: syn-(Methyl,methyl)bimane(68654-22-8)

Safety Data

• WGK Germany: 3
• Hazardous Substances Data: 68654-22-8(Hazardous Substances Data)

Usage

Uses

Used in Organic Synthesis:
syn-(Methyl,methyl)bimane is used as a synthetic intermediate for the development of various organic compounds. Its unique structure and properties make it a valuable building block in the synthesis of complex organic molecules and pharmaceuticals.

InChI:InChI=1/C10H12N2O2/c1-5-7(3)11-8(4)6(2)10(14)12(11)9(5)13/h1-4H3

Upstream product

• 68654-32-0 3,4-dimethyl-4-chloro-2-pyrazolin-5-one 
• 33549-66-5 4,4-dibromo-5-methyl-2,4-dihydro-3H-pyrazol-3-one 
• 60848-28-4 3-methyl-4-phenyl-4-chloro-2-pyrazolin-5-one 
• 74235-66-8 1,2-dimethylene-4,4'-bis(3-methyl-4-chloro-2-pyrazolin-5-one) 
• 100130-07-2 4-bromo-3,4-dimethylpyrazol-5-one 
• 107-03-9 1-thiopropane 
• 71418-44-5 monobromobimane 
• 609-14-3 2-acetylpropanoic acid ethyl ester 
• 60178-92-9 4-methyl-5-oxo-2,5-dihydro-1H-pyrazole-3-carboxylic acid ethyl ester 
• 759-65-9 diethyl oxalpropionate 
• 6628-22-4 3,4-dimethyl-4-chloro-2-pyrazolin-5-one 
• 79746-70-6 3-(carboethoxy)-4-chloro-4-methyl-2-pyrazolin-5-one 
• 79746-68-2 3-(carboethoxy)-4,4-dichloro-2-pyrazolin-5-one 

Downstream Products

• 76421-73-3 Monochlorobimane 
• 76421-90-4 9,10-dioxa-syn-(aminomethyl,methyl)(methyl,methyl)bimane 
• 74235-81-7 9,10-dioxa-syn-(bromomethyl, methyl)(methyl,phenyl)bimane 
• 74235-89-5 9,10-dioxa-anti-(methyl,methyl)(methyl,phenyl)bimane 
• 220357-74-4 9,10-dioxa-syn-(methyl,phenyl)(methyl,methyl)bimane 
• 74235-78-2 9,10-dioxa-anti-(bromomethyl,methyl)(methyl,methyl)bimane 
• 68654-32-0 3,4-dimethyl-4-chloro-2-pyrazolin-5-one 

Relevant articles and documents

Visible Light Activation of Nucleophilic Thiol-X Addition via Thioether Bimane Photocleavage for Polymer Cross-Linking

On-demand photo-uncaging of reactive thiols have been employed in engineering biomaterial scaffolds for regulation of cellular activities. A drawback of the current photo-uncaging chemistry is the utilization of high energy UV light or 2-photon laser light, which may be harmful to cells and cause undesired side reactions within the biological environment. We introduce an effective approach for the caging of thiol using monobromobimane, which can be removed under irradiation of light at = 420 nm and in the presence of electrophiles, such as acrylate, propiolate and maleimide, for trapping of the newly release thiol. This chemical approach can be used in visible light-induced polymer coupling and cross-linking for the preparation of cell-laden hydrogels.

Dihalogen and Solvent-Free Preparation of syn- Bimane

Fluorescent bimanes are low molecular weight and low toxicity molecules with applications ranging from biology to LASER dyes. The widespread use of these molecular probes has presumably been stalled by the hazards involved in their current synthetic preparation which involve handling of dangerous halogens like chlorine (gas) and bromine (liq.). The accessibility achieved by the simple and safe dihalogen and solvent-free methodologies described here open the floodgates to additional future practical applications of bimanes.

Highly sensitive detection of cobalt through fluorescence changes in β-cyclodextrin-bimane complexes

A supramolecular complex ofsyn-(methyl,methyl)bimane (1) and β-cyclodextrin demonstrates a sensitive (limit of detection = 0.60 nM) and selective fluorescence turn-off response in the presence of cobalt in aqueous media, with calibration curves enabling quantitation in solution and using filter papers on which bimane and cyclodextrin were adsorbed.1H NMR spectroscopy provides insight into interactions underlying the sensor performance.

The Synthesis and Chemistry of Azolenines. Part 5. Correction of the structure of an Unusual Heterocycle, Described on Two Earlier Occasions as the Pyrano-4H-pyrazole: 3,3a,4,5-Tetramethylpyranopyrazol-6(3aH)-one

A compound, prepared previously by two different methods, and clamed to be the title compound (2), is shown to be the isomer 3,4,7,8-tetramethyl-1,5-diazabicycloocta-3,7-diene-2,6-dione (11a), a known oxopyrazolopyrazolone.Other products from the same and related reactions are also identified and characterised.

Bimanes. 14. Synthesis and Properties of 4,6-Bis(carboalkoxy)-1,5-diazabicycloocta-3,6-diene-2,8-diones . Preparation of the Parent syn-Bimane, syn-(Hydrogen,hydrogen)bimane.

The 3-(carboalkoxy)pyrazolin-5-ones derived from dialkyl oxaloacetates or diethyl α-methyloxaloacetate through reaction with hydrazine can be converted into the strongly fluorescent 4,6-bis(carboalkoxy)-1,5-diazabicycloocta-3,6-diene-2,8-diones 1)B (6), R=CH3 or CH3CH2, R1=CH3, Cl, Br> by base treatment of the corresponding chloro or bromo derivative.The structure of one bis ester, 4,6-bis(carbomethoxy)-3,7-dimethyl-1,5-diazabicycloocta-3,6-diene-2,8-dione , has beendetermined by X-ray crystallography.Lithium bromide and the esters in CH3CN or DMF yield via dealkylation and decarboxylation the corresponding syn-(H,R1)B (11), (R1=H, CH3, Cl, Br, I) or the "mixed" bimanes syn-(EtOOC,R1)(H,R1)B (10, R1=Cl or CH3).A dicarboxylic acid (R1=CH3; LiBr/CH3CN/60 deg C; two COOCH3's) readily decarboxylates.Hydrogenation of halogenated bimanes over Pd/C(AcOH) replaces one or both halogens, the 2H product from syn-(H,Cl)B being the parent syn-bimane, syn-(H,H)B, syn-(COOR,H)B and ICl yield syn-(COOR,I)B, which gives syn-(H,I)B on dealkylation-decarboxylation.Replacement of Cl in syn-(COOCH2CH3,Cl)B by C6H5S(1-) yields syn-(COOCH2CH3,C6H5S)B.Both ester groups and halogens shift absorption and fluorescence maxima to longer wavelengths than those recorded for syn-(CH3,CH3)B.In 1H NMR spectra, the β-hydrogens of the syn-bimane appear at considerably lower fields (7.52-8.21 ppm) than the α-hydrogens (5.42-6.13 ppm).

Bimanes. 10. Photochemical Rearrangement of 1,5-Diazabicycloocta-3,7-diene-2,6-diones (9,10-Dioxa-anti-bimanes)

1,5-Diazabicycloocta-3,7-diene-2,6-diones (9,10-dioxa-anti-bimanes) rearrange quantitatively on irradiation in the 320 nm absorption band to isomeric lactones, one from symmetrical bimanes and two from unsymmetrical bimanes ("mixed" bimanes).The quantum yield of lactone is often high and depends upon bimane substitution and solvent viscosity.Fast intersystem crossing (Huppert et al.), oxygen inhibition of lactone formation, and efficient formation of lactone via a triplet sensitizer implicate the triplet as a key intermediate.The suggested mechanism of lactoneformation involves a twisted ?-?* triplet.

Bimanes. 6. Reactive halogen derivatives of syn- and anti-1,5-diazabicyclo[3.3.0]octadienediones (9,10-dioxabimanes)

The preparation of reactive halogen derivatives of syn- and anti-1,5-diazabicyclo[3.3.0]octadienediones (9,10-dioxabimanes) is accomplished through the intermediate monobromo- and dibromobimanes previously described. Mono- and dihydroxy compounds are produced from the bromides by reaction with wet sodium trifluoroacetate in CH3CN and are used to prepare the (a) monochlorides and dichlorides (SOCl2) and (b) the monofluorides and difluorides (Et2NSF3). Monofunctional halides react with nucleophiles (amines, thiols, carboxylates) to yield direct substitution products, with some reduction accompanying the thiol reaction. Difunctional halides react with excess nucleophile to give direct disubstitution products. syn-Dihalides react with difunctional nucleophiles (actual or potential, e.g., RNH2, S2-, (CN)2C2,CH3)B are markedly affected by the nature of X. Most syn-bromobimanes are nonfluorescent and are moderately photosensitive, due to thermally reversible isomerizations and additional irreversible reactions. syra-Chlorobimanes are nonfluorescent to weakly fluorescent. syn-Monofluoro- and difluorobimanes are strongly fluorescent. At 77 K, the halogenated compounds are all phosphorescent to some extent and many of the syn derivatives are strongly fluorescent.