2443-46-1

Usage

Uses

Used in Organic Chemistry Research:
1,6-Methano[10]annulen is used as a versatile intermediate for the synthesis of novel materials and functionalized derivatives. Its unique structure and reactivity make it a valuable component in the development of new organic compounds with potential applications in various fields.
Used in Pharmaceutical Industry:
1,6-Methano[10]annulen is used as a precursor to various functionalized derivatives, which can be further utilized in the development of new pharmaceutical compounds. Its potential as a building block for the synthesis of novel materials makes it a promising candidate for creating innovative drug molecules.
Used in Organic Electronics:
1,6-Methano[10]annulen is used as a component in the development of organic electronic materials. Its unique structure and reactivity contribute to the creation of new materials with potential applications in electronic devices and systems.
Used in Materials Science:
1,6-Methano[10]annulen is used as a building block for the synthesis of novel materials with potential applications in materials science. Its strained structure and potential reactivity make it an intriguing target for the development of new materials with unique properties and functions.
Used in Synthetic Organic Chemistry:
1,6-Methano[10]annulen is used as a target molecule for synthetic organic chemists seeking to explore new chemical reactions and methodologies. Its strained structure and potential reactivity provide opportunities for the discovery of innovative synthetic pathways and techniques.

InChI:InChI=1/C11H10/c1-2-6-11-8-4-3-7-10(5-1)9-11/h1-8H,9H2

Upstream product

• 39623-24-0 3,4,8,9-Tetrabrom-tricyclo<4.4.1.0>undecan 
• 4622-37-1 11-bromotricyclo<4.4.1.0^1,6>undeca-3,8-diene 
• 27714-83-6 tricyclo<4.4.1.0^1,6>undeca-3,8-diene 
• 39623-22-8 (4aα,8aα)-9,9-dichloro-1,4,5,8-tetrahydro-4a,8a-methanonaphthalene 
• 87362-36-5 2,3-Bis-((2Z,5Z)-bicyclo[5.4.1]dodeca-1⁽¹¹⁾,2,5,7,9-pentaen-4-ylidene)-succinonitrile 
• 15825-93-1 2,7-dibromo-1,6-methano[10]annulene 
• 68-12-2 N,N-dimethyl-formamide 
• 50785-96-1 1,6-divinylcyclohepta-1,3,5-triene 
• 30234-90-3 4,9-methano[11]annulenone 
• 87362-35-4 ((2Z,5Z)-Bicyclo[5.4.1]dodeca-1⁽¹¹⁾,2,5,7,9-pentaen-4-ylidene)-bromo-acetonitrile 
• 87362-34-3 ((2Z,5Z)-Bicyclo[5.4.1]dodeca-1⁽¹¹⁾,2,5,7,9-pentaen-4-ylidene)-acetonitrile 
• 298214-58-1 1,6-bis(1-hydroxyethyl)cyclohepta-1,3,5-triene 
• 73875-00-0 1,1'-(cyclohepta-3,5,7-triene-1,3-diyl)diethanone 
• 115163-03-6 (1R,4S,4aS,8aR)-1,4-Diisothiocyanato-1,4-dihydro-4a,8a-methano-naphthalene 

Downstream Products

• 83693-19-0 C₁₉H₁₅Br₂N₃O₂ 
• 6130-41-2 (7S,10R)-7,10-Dibromo-bicyclo[4.4.1]undeca-1,3,5,8-tetraene 
• 15825-93-1 2,7-dibromo-1,6-methano[10]annulene 
• 58853-55-7 2-Methoxy-1,6-methano-<10>annulene 
• 58790-01-5 2-methyl-1,6-methano<10>annulene 
• 118684-46-1 2-nitro-3-(p-tolylsulfonylmethyl)bicyclo<4.4.1>undeca-1,3,5,7,9-pentaene 
• 118684-50-7 (+/-)-2-Nitro-5-(4-nitrobenzyl)bicyclo<4.4.1>undeca-1,3,5,7,9-pentaen 
• 137594-08-2 3-<(triphenylphosphoranylidene)amino>-1,6-methano<10>annulene 
• 137594-21-9 6-(4-Chloro-phenyl)-4-phenyl-3-aza-tricyclo[8.4.1.0^2,7]pentadeca-1⁽¹⁴⁾,2⁽⁷⁾,3,5,8,10,12-heptaene 
• 137594-17-3 4,6-Diphenyl-3-aza-tricyclo[8.4.1.0^2,7]pentadeca-1⁽¹⁴⁾,2⁽⁷⁾,3,5,8,10,12-heptaene 
• 137594-15-1 4-(4-Chloro-phenyl)-6-phenyl-3-aza-tricyclo[8.4.1.0^2,7]pentadeca-1⁽¹⁴⁾,2⁽⁷⁾,3,8,10,12-hexaene 
• 137594-16-2 6-(4-Chloro-phenyl)-4-phenyl-3-aza-tricyclo[8.4.1.0^2,7]pentadeca-1⁽¹⁴⁾,2⁽⁷⁾,3,8,10,12-hexaene 
• 137594-14-0 4,6-Diphenyl-3-aza-tricyclo[8.4.1.0^2,7]pentadeca-1⁽¹⁴⁾,2⁽⁷⁾,3,8,10,12-hexaene 
• 137594-27-5 2,4-diphenyl-5,10-methanocyclodecapyridine 

Relevant academic research and scientific papers

Relative Thermodynamic Stabilities of 1,6-Methanoannulene, Dinorcaradiene, and the1,6-Methanoannulene Anion Radical

The enthalpies of reaction of both the solvated and solid salts of potasssium 1,6-metanoannulene (M10) anion radical were measured with calorimetric techniques.These measurements show that anion radical of M10 has suprising degree of thermodynamic stability.The heat of formation of K+M10-*(s) from gas-phase potassium and gas-phase hydrocarbon (-61.9 kcal/mol) is about 16 kcal/mol more negative than that for the solid potassium salt of the naphthalene anion radical.Combustion experiments were used to show that the open form of M10 is about 5.7 kcal/mol lower in energy than dinorcaradiene.

A convenient synthetic method for preparing 2,5-disubstituted 1,6- methano[10]annulenes from 1,6-diacetylcyclohepta-1,3,5-triene

The reaction of 1,6-diacetylcyclohepta-1,3,5-triene with various Grignard reagents gave high yields of addition products 5, which were treated with a catalytic amount of p-toluenesulfonic acid or pyridinium p- toluenesulfonate to afford 2,5-disubstituted 2,3-dihydro-1,6- methano[10]annulenes 6 via 1,6-bis(1-substituted vinyl)cyclohepta-1,3,5- trienes 8 and 2,5-disubstituted 3,4-dihydro-1,6-methano[10]annulenes 9. On the other hand, reactions under more forcing conditions gave the rearrangement products: 4,7-disubstituted 1,2-benzocyclohepta-1,3-dienes 7. The oxidation of 6 with 2,3-dichloro-5,6-dicyano-1,4-benzoquinone gave the 2,5-disubstituted 1,6-methano[10]annulens 4 in moderate-to-good yields. Conversion from 5 into 4 can be achieved by a one-flask procedure, providing a convenient synthetic method for preparing the title annulenes, particularly 2,5-diaryl ones. The reaction mechanism from 8 to 6, 7, and 9 is discussed on the basis of semiempirical molecular orbital calculations.

Base-promoted Eliminations within Halogenated Propellene Frameworks

The reactions of halogenated propellenes with potassium t-butoxide have been investigated.Propelladiene 9,9-dichloro-1,4,5,8-tetrahydro-4a,8a-methanonaphthalene affords 1,6-methanoannulene, 4-methylazulene, and 5H-benzocycloheptene, while the related tetracyclic compound 1,1,8,8-tetrachloro-1a,2,3,6,7,7a-hexahydro-2a,6a-methano-1H-cyclopropanaphthalene reacts to give 12-chlorotricyclo3,5>dodeca-1,3(5),6,8,10-pentaene.Treatment of 8,8-dichloro-2,3,4,7-tetrahydro-3a,7a-methano-1H-indene with the same base produced a mixture of the chlorodiene 8-chloro-2,3-dihydro-3a,7a-methano-1H-indene, azulene, and 4-methylazulene.The structure of the chlorodiene was established by an X-ray crystallographic study of its Diels-Alder adduct with 4-phenyl-4H-1,2,4-triazole-3,5-dione.While reaction of tetracycle 1,1,syn-8-trichloro-1a,2,3,6,7,7a-hexahydro-2a,6a-methano-1H-cyclopropanaphthalene with base failed to produce any characterisable products, under the same conditions epimer 1,1,anti-8-trichloro-1a,2,3,6,7,7a-hexahydro-2a,6a-methano-1H-cyclopropanaphthalene was converted into the cycloproparene tricyclo3,5>dodeca-1,3(5),6,8,10-pentaene.Mechanistic proposals which account for the observed conversions have been advanced and are supported by 13C-labelling studies.The initial steps in most of the reaction pathways of the substrates are probably 1,4-elimination processes involving abstraction of an allylic hydrogen, fragmentation of the strained propellene ?-bond, and ejection of the halogen in an endo-relationship to the abstracted proton.The primary product of these processes, bridgehead dienes such as bicycloundeca-1,3,6(11),8-tetraene, 4,4,12-trichlorotricyclo3,5>dodeca-1(11), 7(12),9-triene and 10-chlorobicyclodeca-1,3,6(10)-triene, then undergo further reaction involving, amongst other things, 1,3-prototropic shifts.Attempts to probe the mode of formation of the C11-4-methylazulene from the C10-precursor 8,8-dichloro-2,3,4,7-tetrahydro-3a,7a-methano-1H-indene have uncovered a novel methylation reaction of azulene by the dimsyl anion.

Studies in the Cycloproparene Series: Approaches to Bicycloocta-1,3,6-triene, a Cyclopropa-Fused Cycloheptatriene

The dichloromethylene-bridged annulene (5) is available in four steps (47percent) from 1,4,5,8-tetrahydronaphthalene (11) via the dibromide (15); the minor (5percent) product of dehydrobromination of (15) is 2-bromo-9,9-dichloro-1,4-dihydro-4a,8a-methanonaphthalene (16).Dichlorocarbene adds to the norcaradiene form of (5) to give adduct (6) with 80percent efficiency.Diene (6) resists both ?4 + ?2> cycloadditions and reductive dechlorination.Neither (5) nor parent 1,6-methanoannulene (18) adds methylene from Simmons-Smith cyclopropanation procedures.

Unexpected Course of Thiocyanation of 1,6-Methanoannulene. Elimination of Thiocyanogen from a Diisothiocyanate

The isolation of the syn,syn-adduct in the reaction of 1,6-methanoannulene (1) with the bulky pseudo-halogen (SCN)2 indicates a preferred exo attack of electrophiles on 1, in spite of a possible steric interference with the methylene bridge.The formation of the unexpected isothiocyanates 4 and 5 is explained in terms of an addition-isomerization-elimination sequence.The novel elimination of (SCN)2 from a diisothiocyanate is investigated. - Key Words: 1,6-Methanoannulene / Thiocyanogen / Isothiocyanic acid

Electrophilic Substitution in Annulenes. Part 4. Transmission of Substituent Effects in 1,6-Methanoannulene, determined via Protiodesilylation: Evidence for Substantial C(1)-C(6) Transannular Orbital Interaction

The rates of acid-catalysed desilylation of a series of 7-substituted 2-trimethylsilyl-1,6-methanoannulenes have been measured spectrophotometrically at 50 degC using a mixture of aqueous perchloric acid and methanol (2:5 v/v).The substituent effects

SOME GROUP IVB DERIVATIVES OF 1,6-METHANOANNULENE. SYNTHESIS, SUBSTITUENT EFFECTS AND REACTIVITY

Certain Group IVB derivatives of 1,6-methanoannulene have been synthesised, and their 13C nuclear magnetic resonance spectra recorded and assigned, to provide a measure of the substituent effects exerted by metalloid-containing groups in this non-benzenoid aromatic system.Comparisons are made with the corresponding naphthalene and some anthracene derivatives.Protiodemetallations of a number of arylsilanes and -stannanes have been examined, and in protiodestannyletion by CH3CO2H/dioxane at 27 deg C (an electrophilic aromatic substitution) the α- (or 2-) posititon of 1,6-methanoannulene is ca. 35 times as reactive as the α (or 1-) position of naphthalene, whereas in protiodesilylation by CF3CO2H/CH3CO2H at 27 deg C it is ca. 700 times the more reactive.

SYNTHESIS AND ELECTROCYCLISATION OF HENDECAFULVADIENES "AZULENOID" 14?-ANNULENES

The possibilitiy of a 24?-elecrocyclisation has been investigated in the hendecafulvadienes 3 (4); examples of a novel type of bridged 14?-annulenes (6,12,13) have been synthesised and shown to have "azulenoid" character.

Syntheses and Chemical Properties of Heterocyclic-substituted 1,6-Methano-annulenes

Syntheses, chemical and spectroscopic properties of the partly heterocyclic-substituted 1,6-methano-annulenes 2, 3, 4, 7, 8, and 9 are described.

Novel Syntheses of 1,6-Methanoannulene and 4-Methylazulene

Reaction of 11,11-dichlorotricyclo1,6>undeca-3,8-diene (4) with potassium t-butoxide in dimethyl sulphoxide affords 1,6-methanoannulene (9) and 4-methylazulene (10); similar treatment of the dibromopropellane (5) yields the azulene (10), the monobromopropellane (11), but diminished yields of the annulene (9).