About: Carbon Insertion into arachno-6,9-C2B8H14 via Acyl Chlorides. Skeletal Alkylcarbonation (SAC) Reactions: A New Route for Tricarbollides

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About: Carbon Insertion into arachno-6,9-C2B8H14 via Acyl Chlorides. Skeletal Alkylcarbonation (SAC) Reactions: A New Route for Tricarbollides Goto Sponge NotDistinct Permalink

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rdf:type	skos:Concept http://linked.opendata.cz/ontology/domain/vavai/Vysledek
rdfs:seeAlso	http://pubs.acs.org/doi/abs/10.1021/ic401293g
Description	Reactions between arachno-6,9-C2B8H14 (1) and selected acyl chlorides, RCOCl, in the presence of PS (PS = %22proton sponge%22, 1,8-dimethylamino naphthalene) in CH2Cl2 for 24 h at reflux, followed by in situ acidification with concentrated H2SO4 at 0 degrees C, generate a series of neutral alkyl and aryl tricarbollides 8-R-nido-7,8,9-C3B8H11 (2) (where R = CH3, 2a; C2H5, 2b; n-C4H9, 2c; C6H5, 2d; 4-Cl-C6H4, 2e; 4-Br-C6H4, 2f; 4-I-C6H4, 2g; 1-C10H7, 2h; and 2-C10H7, 2i). The best yields were achieved for aryl derivatives (80-95%) while the yields of the corresponding alkyl substituted compounds are lower (60-70%). These skeletal alkylcarbonation (SAC) reactions are consistent with an aldol-type condensation between the RCO group and open-face hydrogen atoms on the dicarbaborane 1, which is associated with the insertion of the carbonyl carbon atom into the structure of arachno-6,9-C2B8H14 (1) under elimination of three extra hydrogen atoms as H2O and HCl. The reactions thus result in an effective R-tricarbaborane cross-coupling. Individual compounds of structure 2 have been purified by chromatography on a silica gel support, using hexane as the mobile phase (R-F = similar to 0.3). Deprotonation agents, such as NEt3, NaOH, NaH, etc., convert tricarbaboranes 2 into the corresponding conjugated anions [8-R-nido-7,8,9-C3B8H10](-) (2(-)) which were isolated as salts with suitable countercations (for example, Et3NH+, Tl+, NEt4+, etc.). The compounds have been characterized by multinuclear (B-11, H-1, and C-13) NMR spectroscopy, mass spectrometry, and elemental analyses. The structures of anions [8-R-nido-7,8,9-C3B8H10](-) (where R = C6H5, 4-I-C6H4 and 1-C10H7; 2a(-), 2g(-), and 2h(-)) and that of the neutral 8-(1-C10H7)-nido-7,8,9-C3B8H11 (2h) have been established by X-ray diffraction analyses. Reactions between arachno-6,9-C2B8H14 (1) and selected acyl chlorides, RCOCl, in the presence of PS (PS = %22proton sponge%22, 1,8-dimethylamino naphthalene) in CH2Cl2 for 24 h at reflux, followed by in situ acidification with concentrated H2SO4 at 0 degrees C, generate a series of neutral alkyl and aryl tricarbollides 8-R-nido-7,8,9-C3B8H11 (2) (where R = CH3, 2a; C2H5, 2b; n-C4H9, 2c; C6H5, 2d; 4-Cl-C6H4, 2e; 4-Br-C6H4, 2f; 4-I-C6H4, 2g; 1-C10H7, 2h; and 2-C10H7, 2i). The best yields were achieved for aryl derivatives (80-95%) while the yields of the corresponding alkyl substituted compounds are lower (60-70%). These skeletal alkylcarbonation (SAC) reactions are consistent with an aldol-type condensation between the RCO group and open-face hydrogen atoms on the dicarbaborane 1, which is associated with the insertion of the carbonyl carbon atom into the structure of arachno-6,9-C2B8H14 (1) under elimination of three extra hydrogen atoms as H2O and HCl. The reactions thus result in an effective R-tricarbaborane cross-coupling. Individual compounds of structure 2 have been purified by chromatography on a silica gel support, using hexane as the mobile phase (R-F = similar to 0.3). Deprotonation agents, such as NEt3, NaOH, NaH, etc., convert tricarbaboranes 2 into the corresponding conjugated anions [8-R-nido-7,8,9-C3B8H10](-) (2(-)) which were isolated as salts with suitable countercations (for example, Et3NH+, Tl+, NEt4+, etc.). The compounds have been characterized by multinuclear (B-11, H-1, and C-13) NMR spectroscopy, mass spectrometry, and elemental analyses. The structures of anions [8-R-nido-7,8,9-C3B8H10](-) (where R = C6H5, 4-I-C6H4 and 1-C10H7; 2a(-), 2g(-), and 2h(-)) and that of the neutral 8-(1-C10H7)-nido-7,8,9-C3B8H11 (2h) have been established by X-ray diffraction analyses. (en)
Title	Carbon Insertion into arachno-6,9-C2B8H14 via Acyl Chlorides. Skeletal Alkylcarbonation (SAC) Reactions: A New Route for Tricarbollides Carbon Insertion into arachno-6,9-C2B8H14 via Acyl Chlorides. Skeletal Alkylcarbonation (SAC) Reactions: A New Route for Tricarbollides (en)
skos:prefLabel	Carbon Insertion into arachno-6,9-C2B8H14 via Acyl Chlorides. Skeletal Alkylcarbonation (SAC) Reactions: A New Route for Tricarbollides Carbon Insertion into arachno-6,9-C2B8H14 via Acyl Chlorides. Skeletal Alkylcarbonation (SAC) Reactions: A New Route for Tricarbollides (en)
skos:notation	RIV/00216275:25310/13:39896342!RIV14-GA0-25310___
http://linked.open...avai/riv/aktivita	I P
http://linked.open...avai/riv/aktivity	I, P(GAP207/11/0705)
http://linked.open...iv/cisloPeriodika	15
http://linked.open...vai/riv/dodaniDat	2014
http://linked.open...aciTvurceVysledku	Růžička, Aleš Padělková, Zdeňka
http://linked.open.../riv/druhVysledku	J - Článek v odborném periodiku
http://linked.open...iv/duvernostUdaju	S - Úplné a pravdivé údaje nepodléhající ochraně podle zvláštních právních předpisů
http://linked.open...titaPredkladatele	Univerzita Pardubice / Fakulta chemicko-technologická
http://linked.open...dnocenehoVysledku	64262
http://linked.open...ai/riv/idVysledku	RIV/00216275:25310/13:39896342
http://linked.open...riv/jazykVysledku	eng - angličtina
http://linked.open.../riv/klicovaSlova	series; derivatives; cage-carbon; borane anions; monocarbon carboranes; metallatricarbaborane complexes; high-yield; 12-vertex ferratricarbollides; structural characterizations; magnetic-resonance-spectroscopy (en)
http://linked.open.../riv/klicoveSlovo	derivatives series 12-vertex ferratricarbollides borane anions cage-carbon high-yield metallatricarbaborane complexes monocarbon carboranes structural characterizations magnetic-resonance-spectroscopy
http://linked.open...odStatuVydavatele	US - Spojené státy americké
http://linked.open...ontrolniKodProRIV	[3CFBC7DC6F0C]
http://linked.open...i/riv/nazevZdroje	Inorganic Chemistry
http://linked.open...in/vavai/riv/obor	CA
http://linked.open...ichTvurcuVysledku	2 (xsd:int)
http://linked.open...cetTvurcuVysledku	5 (xsd:int)
http://linked.open...vavai/riv/projekt	Carborane-modified iron-arene complexes
http://linked.open...UplatneniVysledku	2013
http://linked.open...v/svazekPeriodika	52
http://linked.open...iv/tvurceVysledku	Bakardjiev, Mario Holub, Josef Padělková, Zdeňka Růžička, Aleš Štíbr, Bohumil
http://linked.open...ain/vavai/riv/wos	000322863300091
issn	0020-1669
number of pages	7 (xsd:int)
http://bibframe.org/vocab/doi	10.1021/ic401293g
http://localhost/t...ganizacniJednotka	25310

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