scholarly journals Studies of Some Strained Organic Molecules

2021 ◽  
Author(s):  
◽  
Carissa Susan Jones
Keyword(s):  
Organic Molecules ◽  
Charge Transfer Complex ◽  
Ring Expansion ◽  
Chloride Anion ◽  
The Novel ◽  
Enol Ethers ◽  
X Ray ◽  
Dimethyl Acetamide ◽  
A Charge ◽  
Alternative Routes

<p>The characterisation of rare examples of C1-substituted cyclopropanaphthalenes has been achieved with silanes (104) and (112) by employing the C1 anion (106). With toluene, N,N-dimethylacetamide, and cyclopropanaphthalene (58) this same anion gives the novel 6-methyl-7H-dibenzo[b,g]fluorene (179), a formal dimer of cycloproparene (58). Hydrocarbon (179) is the sole dibenzo[b,g]hydrocarbon characterised and this has required extensive spectroscopic study with confirmation from X-ray analysis. A possible new route to alkylidenecyclopropanaphthalenes (114) employing lithiate (170) and either cycloproparene (58) or its disilyl analogue (105) was found to offer no advantage over known procedures. Application of the protocols embodied in this procedure to brominated synthons (114o) and (114p) has afforded novel pi-extended methylidene compounds (197a) and (199) in low yield. Cyclopentadienylidene (197a) has also been prepared in better yield from benzophenone-containing methylidenecycloproparene (200). Initial attempts to obtain (200) from anion (193) and N,N-dimethylbenzamide were unsuccessful and gave instead the new phenol (114q). The first acylcycloproparenes (189) and (202) have been obtained in modest yield from anion (103) and N,N-dimethyl-acetamide, and -benzamide. With N,N-dimethyl-carbamoyl chloride anion (103) gives the bis-amide (205). With hydrochloric acid these acylcycloproparenes give rise to 2,3-disubstituted naphthalenes rather than 2-substituted naphthalenes that typically arise from protonation at the aromatic ring. Thermolysis leads to ring expansion and naphthofuran formation. Enolate formation from the 1-acyl-cyclopropanaphthalenes (189) and (202) and anion capture at oxygen affords the first cyclopropanaphthalenylidene enol ethers (219) and (220). 1H-Cyclopropa[b]naphthalene-3,6-dione (154) adds buta-1,3-diene across the enedione Pi-bond to give the tetrahydrocyclopropanthraquinone (160). Enolisation of (160) provides phenolate (234) that can be diverted to ether (229) or oxidised to the dihydroanthraquinone (230). Dehydrogenation of (229) is readily achieved and gives the first anthraquinone of the cycloproparene series 1H-cyclopropa[b]anthracene-3,8-dione (162); quinone (162) is only the second cyclopropaquinone to have been characterised. Alternative routes to quinone (162) and its 3,8-dimethoxy analogue (163) have been examined with a view to providing the first alkylidenecyclopropanthracenes. The first examples of cross-conjugated dithiole-containing cycloproparenes, (169) and (267), have been prepared from cyclopropanthraquinone (162) but they are unstable solids. The pi-extended dithiole-containing methylidene compound (273) has been prepared in good yield from Wittig-Horner olefination of the benzoylmethylidene compound (200). Evidence was obtained to support the formation of a charge-transfer complex from it. Ketones already carrying a conjugated dithiole moiety participate in the Peterson olefination with the alpha-silyl anion (106) and give the new pi-extended methylidenecyclopropanaphthalenes (274) and (277) of limited stability.</p>

scholarly journals Studies of Some Strained Organic Molecules

2021 ◽  
Author(s):  
◽  
Carissa Susan Jones
Keyword(s):  
Organic Molecules ◽  
Charge Transfer Complex ◽  
Ring Expansion ◽  
Chloride Anion ◽  
The Novel ◽  
Enol Ethers ◽  
X Ray ◽  
Dimethyl Acetamide ◽  
A Charge ◽  
Alternative Routes

<p>The characterisation of rare examples of C1-substituted cyclopropanaphthalenes has been achieved with silanes (104) and (112) by employing the C1 anion (106). With toluene, N,N-dimethylacetamide, and cyclopropanaphthalene (58) this same anion gives the novel 6-methyl-7H-dibenzo[b,g]fluorene (179), a formal dimer of cycloproparene (58). Hydrocarbon (179) is the sole dibenzo[b,g]hydrocarbon characterised and this has required extensive spectroscopic study with confirmation from X-ray analysis. A possible new route to alkylidenecyclopropanaphthalenes (114) employing lithiate (170) and either cycloproparene (58) or its disilyl analogue (105) was found to offer no advantage over known procedures. Application of the protocols embodied in this procedure to brominated synthons (114o) and (114p) has afforded novel pi-extended methylidene compounds (197a) and (199) in low yield. Cyclopentadienylidene (197a) has also been prepared in better yield from benzophenone-containing methylidenecycloproparene (200). Initial attempts to obtain (200) from anion (193) and N,N-dimethylbenzamide were unsuccessful and gave instead the new phenol (114q). The first acylcycloproparenes (189) and (202) have been obtained in modest yield from anion (103) and N,N-dimethyl-acetamide, and -benzamide. With N,N-dimethyl-carbamoyl chloride anion (103) gives the bis-amide (205). With hydrochloric acid these acylcycloproparenes give rise to 2,3-disubstituted naphthalenes rather than 2-substituted naphthalenes that typically arise from protonation at the aromatic ring. Thermolysis leads to ring expansion and naphthofuran formation. Enolate formation from the 1-acyl-cyclopropanaphthalenes (189) and (202) and anion capture at oxygen affords the first cyclopropanaphthalenylidene enol ethers (219) and (220). 1H-Cyclopropa[b]naphthalene-3,6-dione (154) adds buta-1,3-diene across the enedione Pi-bond to give the tetrahydrocyclopropanthraquinone (160). Enolisation of (160) provides phenolate (234) that can be diverted to ether (229) or oxidised to the dihydroanthraquinone (230). Dehydrogenation of (229) is readily achieved and gives the first anthraquinone of the cycloproparene series 1H-cyclopropa[b]anthracene-3,8-dione (162); quinone (162) is only the second cyclopropaquinone to have been characterised. Alternative routes to quinone (162) and its 3,8-dimethoxy analogue (163) have been examined with a view to providing the first alkylidenecyclopropanthracenes. The first examples of cross-conjugated dithiole-containing cycloproparenes, (169) and (267), have been prepared from cyclopropanthraquinone (162) but they are unstable solids. The pi-extended dithiole-containing methylidene compound (273) has been prepared in good yield from Wittig-Horner olefination of the benzoylmethylidene compound (200). Evidence was obtained to support the formation of a charge-transfer complex from it. Ketones already carrying a conjugated dithiole moiety participate in the Peterson olefination with the alpha-silyl anion (106) and give the new pi-extended methylidenecyclopropanaphthalenes (274) and (277) of limited stability.</p>

Synthesis and X-Ray Study of a Charge-Transfer Complex of Pyrido[2,3-H]pyrrolo[1,2-a]quinoxaline - 7,7,8,8-Tetracyano-p-quinodimethane (1:1)

1988 ◽  
Vol 41 (6) ◽  
pp. 971 ◽  
Author(s):  
B Viossat ◽  
NH Dung ◽  
JC Daran ◽  
JC Lancelot ◽  
M Robba
Keyword(s):  
Charge Transfer ◽  
Charge Transfer Complex ◽  
Three Dimensional ◽  
Direct Methods ◽  
Title Complex ◽  
Full Matrix ◽  
X Ray ◽  
Donor And Acceptor ◽  
A Charge ◽  
Tcnq Molecule

The structure of the title complex has been determined by a three-dimensional X-ray analysis. Triclinic crystals in space group Pī have lattice parameters a 7.0912(8), b 7.692(2), c 19.119(3)Ǻ, α 87.09(2),β 84.01(1),γ 82.72(1)°, Z 2. The structure was solved by means of direct methods and refined by full matrix least squares to R 0.039 and Rw 0.035 for 1671 observed reflections. Almost parallel tetracyanoquinodimethane (tcnq ) and pyridopyrroloquinoxaline molecules are stacked alternately along the a axis. Differences in C-C distances for the complexed tcnq molecule suggest a certain amount of charge-transfer interaction between donor and acceptor molecules.

Radikal-markierte Metallocene (M = Fe, Co). Metallocenylen verbrückte Bis(3-imidazolin-l-oxyle) / Radical Labeled M etallocenes (M = Fe, Co). M etallocenylene B ridged B is(3-im idazolin-l-oxyls)

2001 ◽  
Vol 56 (7) ◽  
pp. 563-570
Author(s):  
Harald Dialer ◽  
Kurt Polbom ◽  
Wolfgang Beck
Keyword(s):  
Charge Transfer ◽  
Radical Anion ◽  
Room Temperature ◽  
Lithium Salt ◽  
Charge Transfer Complex ◽  
Magnetic Measurements ◽  
X Ray Diffraction ◽  
X Ray ◽  
A Charge ◽  
Different Sources

Abstract Radical Labeled M etallocenes (M = Fe, Co). M etallocenylene B ridged B is(3-im idazolin-l-oxyls) The addition of the lithium salt of the silyl protected hydroxylamine 1-hydroxy-2,2,4,5,5-pentamethyl-3-imidazoline (1) to 6 ,6 -dimethylfulvalene gives the lithium cyclopentadienide 2 from which the 1,1 '-substituted ferrocene and cobaltocinium derivatives 3 and 4 were obtained. Deprotection and oxidation of 3 and 4 afford the metallocenylene bridged bis(3-imidazolin-l-oxyls) 5 and 7. The ferrocene bridged diradical 5 forms with DDQ a charge transfer complex 8 . The complexes 5 and 7 were characterized by X-ray diffraction and by their EPR spectra. Magnetic measurements show at room temperature two independent spins for 5 and 7 and four unpaired electrons for 8 , the latter arising from three different sources [Fe(III) low spin d5, two nitroxides and DDQ- radical anion].

scholarly journals Structural Study of the Methylnaphthazarins. X-Ray Structure of the Tetramethylnaphthazarin, a Charge Transfer Complex

1986 ◽  
Vol 59 (12) ◽  
pp. 3957-3961 ◽  
Author(s):  
José-Gonzalo Rodriguez ◽  
Alfonso De Pablo ◽  
Pilar Smith-Verdier ◽  
Feliciana Florencio ◽  
Severino Garcia-Blanco
Keyword(s):  
Charge Transfer ◽  
Structural Study ◽  
Charge Transfer Complex ◽  
X Ray ◽  
A Charge

scholarly journals Intermolecular interactions and charge transfer in the 2:1 tetrathiafulvalene bromanil complex, (TTF)2-BA

2011 ◽  
Vol 67 (3) ◽  
pp. 244-249 ◽  
Author(s):  
Pilar García-Orduña ◽  
Slimane Dahaoui ◽  
Claude Lecomte
Keyword(s):  
Crystal Structure ◽  
Phase Transition ◽  
Charge Transfer ◽  
Room Temperature ◽  
Charge Transfer Complex ◽  
Structural Phase ◽  
X Ray Diffraction ◽  
X Ray ◽  
Donor And Acceptor ◽  
A Charge

The crystal structure of the 2:1 charge-transfer complex of tetrathiafulvalene [2,2′-bis(1,3-dithiolylidene)] and bromanil (tetrabromo-1,4-benzoquinone) [(TTF)2-BA, (C6H4S4)2–C6Br4O2] has been determined by X-ray diffraction at room temperature, 100 and 25 K. No structural phase transition occurs in the temperature range studied. The crystal is made of TTF–BA–TTF sandwich trimers. A charge-transfer estimation between donor and acceptor (0.2 e) molecules is proposed in comparison to the molecular geometries of TTF–BA and TTF and BA isolated molecules. Displacement parameters of the molecules have been modeled with the TLS formalism.

ChemInform Abstract: Synthesis and X-Ray Study of a Charge-Transfer Complex of Pyrido(2,3-h)pyrrolo(1,2-a)quinoxaline-7,7,8,8-Tetracyano-p-quinodimethane (1:1)

ChemInform ◽  
1989 ◽  
Vol 20 (3) ◽  
Author(s):  
B. VIOSSAT ◽  
NGUYEN-HUY DUNG NGUYEN-HUY DUNG ◽  
J. C. DARAN ◽  
J. C. LANCELOT ◽  
M. ROBBA
Keyword(s):  
Charge Transfer ◽  
Charge Transfer Complex ◽  
X Ray ◽  
A Charge

High Resolution Replication of Organoclay Surfaces

1982 ◽  
Vol 40 ◽  
pp. 576-577
Author(s):  
W. W. Barker ◽  
W. E. Rigsby ◽  
V. J. Hurst ◽  
W. J. Humphreys
Keyword(s):  
Clay Mineral ◽  
Organic Molecule ◽  
Organic Molecules ◽  
X Ray Diffraction ◽  
Xrd Pattern ◽  
X Ray ◽  
Naturally Occurring ◽  
Silicate Layers ◽  
Mineral Identification

Experimental clay mineral-organic molecule complexes long have been known and some of them have been extensively studied by X-ray diffraction methods. The organic molecules are adsorbed onto the surfaces of the clay minerals, or intercalated between the silicate layers. Natural organo-clays also are widely recognized but generally have not been well characterized. Widely used techniques for clay mineral identification involve treatment of the sample with H2 O2 or other oxidant to destroy any associated organics. This generally simplifies and intensifies the XRD pattern of the clay residue, but helps little with the characterization of the original organoclay. Adequate techniques for the direct observation of synthetic and naturally occurring organoclays are yet to be developed.

Ten-Vertex Polyhedral Monocarbaborane Chemistry. The Novel High-Yield Formation of the Ten-Vertex closo Compound [6-(PMe2Ph)-closo-1-CB9H9] from the Thermolysis of [8,8-(PMe2Ph)2-nido-8,7-PtCB9H11]

1993 ◽  
Vol 58 (12) ◽  
pp. 2924-2935 ◽  
Author(s):  
Jane H. Jones ◽  
Bohumil Štíbr ◽  
John D. Kennedy ◽  
Mark Thornton-Pett
Keyword(s):  
Nmr Spectroscopy ◽  
Diffraction Analysis ◽  
High Yield ◽  
Monoclinic Space Group ◽  
The Novel ◽  
X Ray Diffraction ◽  
Metal Centre ◽  
X Ray ◽  
Yield Formation ◽  
Boiling Toluene

Thermolysis of [8,8-(PMe2Ph)2-nido-8,7-PtCB9H11] in boiling toluene solution results in an elimination of the platinum centre and cluster closure to give the ten-vertex closo species [6-(PMe2Ph)-closo-1-CB9H9] in 85% yield as a colourles air stable solid. The product is characterized by NMR spectroscopy and single-crystal X-ray diffraction analysis. Crystals (from hexane-dichloromethane) are monoclinic, space group P21/c, with a = 903.20(9), b = 1 481.86(11), c = 2 320.0(2) pm, β = 97.860(7)° and Z = 8, and the structure has been refined to R(Rw) = 0.045(0.051) for 3 281 observed reflections with Fo > 2.0σ(Fo). The clean high-yield elimination of a metal centre from a polyhedral metallaborane or metallaheteroborane species is very rare.

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