A Rapid Catalytic Preparation of Sodamide in Liquid Ammonia and Some of its Uses in the Preparation of Acetylenic Materials

Vaughn, Thomas H.; Vogt, R. R.; Nieuwland, J. A.

doi:10.1021/ja01325a038

Cited by 105 publications

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“…[17] It worsens the situation that the reaction is catalytically activated, when iron, nickel, cobalt, platinum, or their compounds are present. [18] These are usual contaminants in graphite and graphene, [19]…”

Section: Side Reaction Of Gaseous Ammonia and Alkali Metalsmentioning

confidence: 99%

Improved Alkali Intercalation of Carbonaceous Materials in Ammonia Solution

Márkus

Szirmai

Kollarics

et al. 2019

Physica Status Solidi (b)

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Alkali‐intercalated graphite compounds represent a compelling modification of carbon with significant application potential and various fundamentally important phases. The intercalation of graphite with alkali atoms (Li and K) using liquid ammonia solution as a mediating agent is reported. Alkali atoms dissolve well in liquid ammonia, which simplifies and speeds up the intercalation process, and it also avoids the high temperature formation of alkali carbides. Optical microscopy, Raman, and electron spin‐resonance spectroscopy attest that the prepared samples are highly and homogeneously intercalated to a level approaching stage‐I intercalation compounds. The method and the synthesis route may serve as a starting point for the various forms of alkali‐atom‐intercalated carbon compounds (including carbon nanotubes and graphene), which can be exploited in energy storage and further chemical modifications.

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Section: Side Reaction Of Gaseous Ammonia and Alkali Metalsmentioning

confidence: 99%

Improved Alkali Intercalation of Carbonaceous Materials in Ammonia Solution

Márkus

Szirmai

Kollarics

et al. 2019

Physica Status Solidi (b)

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“…; die Alkine C und D analog dazu aus 1-Amino-1-ethinyl-cyclohexan [37,38] und Aceton bzw. Cyclohexanon.…”

Section: -In (A) Und 1-(3-amino-3-methyl-but-1-inyl)-cyclohexan-1-olunclassified

Platin(0)‐Komplexe mit amino‐substituierten Alkinen: Neue Metallorganische Bausteine für supramolekulare Architekturen und „Kristall‐Engineering”︁

Walther¹,

Heubach²,

Böttcher³

et al. 2002

Z. anorg. allg. Chem.

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Professor Lothar Beyer zum 65. Geburtstag gewidmet Inhaltsu È bersicht. Homoleptische Bis(alkin)platin(0)-Verbindungen mit NH 2 -bzw. NH 2 -und OH-Substituenten sind durch Reaktion von Pt(cod) 2 mit Alkinen als stabile Verbindungen herstellbar und als variable Bausteine fu È r supramolekulare Verba È nde verwendbar. Die Kristallstrukturanalysen von Bis(2-Amino-2,5-dimethyl-5-hydroxy-hex-3-in)platin (0) (1) und von Bis(1-(3-Amino-3-methyl-but-1-inyl)-cyclohexan-1-ol)platin(0) (2) zeigen, dass Pt 0 tetraedrisch von den vier sphybridisierten Kohlenstoffatomen der Alkine umgeben ist. Trotz gleicher Bindungsla Èngen und -winkel der PtC 4 -Tetraeder ist die supramolekulare Verknu È pfung verschieden. Wa Èh-rend in 1 polymere Stra Ènge gebildet werden, in denen die Bis(alkin)-Platin(0)-Einheiten durch (OH) 2 (NH 2 ) 2 -Tetraeder verknu È pft sind, bildet 2 nur ein Dimer, das u È ber ein H-Bru È -ckennetzwerk von vier OH-und zwei NH 2 -Gruppen verbunden ist.Auch Alkin-Platin(0)-Komplexe mit kationischen Alkinliganden, die Ammoniumsubstituenten an den Alkinen enthalten, sind als thermisch stabile Verbindungen isolierbar. Die Kristallstrukturanalyse von [Cl(FH + )Pt(cod)] 4 (8) weist aus, dass vier molekulare Einheiten einen Kubus bilden, mit je vier NH 3 + -Gruppen und Cl ± an den Ecken, die durch Wasserstoffbru È cken zusammengehalten werden. Im Bis-(alkin)Platin(0)-Komplex [Cl 1,5 (FH + ) 1,5 (F) 0,5 Pt] (9) sind nur 1,5 von zwei NH 2 -Gruppen protoniert, und ein Netzwerk von Wasserstoffbru È cken verknu È pft vier Bis(alkin)Platin(0)-Einheiten miteinander. (cod: cycloocta-1,5-dien, F: 1-(Trimethylsilylethinyl)-1-amino-cyclohexan). Platinum(0) Complexes with Amino-Substituted Alkynes: Novel Organometallic Building Blocks for Supramolecular Architectures and ªCrystal EngineeringºAbstract. Homoleptic Bis(alkyne)platinum(0) compounds containing either NH 2 -or NH 2 -/OH-substituents are formed by reaction of Pt(cod) 2 with alkynes as stable compounds. They can be used as variable building blocks for supramolecular networks. The crystal structure analyses of Bis(2-amino-2,5-dimethyl-5-hydroxy-hex-3-yne)platinum(0) (1) and of Bis(1-(3-amino-3-methyl-but-1-inyl)-cyclohexane-1-ol)platinum(0) (2) exhibit that the low-valent Pt atom is tetrahedrally surrounded by the four sp-hybridizated carbonatoms of the alkynes. Despite the fact that the bond lengths and -angles of the PtC 4 units are equal, the supramolecular structures are different. While in 1 polymer strands are formed in which the bis-(alkyne)-Pt 0 units are connected by (OH) 2 (NH 2 ) 2 -tetrahedrons, 2 yields only a dimer containing a network of four OHand two NH 2 -groups.Platinum(0) complexes with cationic alkynes bearing ammonium substituents can be isolated as thermal stable compounds. The X-ray structures of [Cl(FH + )Pt(cod)] 4 (8) reveals that four molecular units form a cube with both four NH 3 + groups and Cl ± at the corners connected by hydrogen bridges. In the bis(alkyne)Pt 0 complex [Cl 1.5 (FH + ) 1.5 (F) 0.5 Pt] (9) only 1,33 of two NH 2 groups are proto...

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“…The method can be used for the preparation of various ethynylthiophenes under mild conditions [38]. Similarly, phenylacetylene is produced from a-chlorostyrene [39], and 1,3,5-triethynylbenzene (12) can be obtained in 60 % yield from ( l l ) , which does not react with boiling methanolic potassium hydroxide [40]. Organometallic compounds, especially those of alkali metals, are most versatile in elimination reactions of the type under consideration.…”

Section: E L I M I N a T I O N By A L K A L I M E T A L A M I D E Smentioning

confidence: 99%

“…3-Bromo-cis-cinnamic acid undergoes fragmeiitation about 100 times more rapidly than its stereoisonw I (39), and hence presumably by a different mechanism (cf. Section III.A.1) [72].…”

Section: )mentioning

confidence: 99%

Eliminations from Olefins

Köbrich

1965

Angew. Chem. Int. Ed. Engl.

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increase in the rate of reaction with increasing dielectric constant of the solvent found in the acid-catalysed hydrolysis of esters [1,221. VI. Concluding RemarksDiscussion of the importance of the mobility of protons in the course of chemical reactions has been attempted in this paper, using acid-catalysed esterification as an example. Conditions are considered which are significant, not only in esterification, but in proton-catdlysed [22] K. J. Laidler and P. A. Lnndskroener, Trans. Faraday SOC. 52, 200 (1956).reactions generally. Our observations are necessarily incomplete and have the character of an approximation. However, we believe that the great importance of protons in chemistry justifies our attempted interpretation.We wish to thank Prof. G. Scheibe for his helpful interest in this work. We are also indebted to thz Deutsche Forschungsgemeinschaft, the Fonds der Chemischen Indw strie, and the Badische Anilin-und Sodafabrik for financially and materially supporting our investigations on "Protonic States in Chemistry".Eliminatiotts from olefiny are very ofren initiated by bases, and usually lead to formation of acetylene derivatives. In view of the numerous side-reactions and subsequent additions or rearrangements observed, the nature of the base used is of considerable significance. Organometallic bases are very versatile. In addition to dehydrohalogenation, dehalogenation by metals, and also thermolytic and photolytic eliminations (e.g. the retrodiene reaction with exchange of substituents) are discussed. Elimination from low-membered cyclic olefins yields cycloalkynes having strained ring-systems, and the exis fence of these can be denioiistrated by trapping them. The mechanisms known for @-elimination ( E 2 , E l and ElcB) occur also in the case of olefins; howeverdue to the sp2-hybridization of the carbon atoms taking partthey are realized with diflerent rates of reaction relative to saturated corm pounds. a-Eliminations from olefines having aryl residues in the @-position lead to formation of arylacetylenes by rearrangement of the carbon skeleton. The mechanism of this reaction, which is known as the Fritsch-Buttenberg-Wiechell rearrangement, is discussed in considerable detail, and several variations of the reaction are considered. According to presentday knowledge carbenes are involved in r-eliminations only when both @-positions of the olefin are occupied by aliphatic substituents, or when they are occupied by aromatic residues where rearrangement to acetylenes is impossible for steric reasons (as for example with 9-chlorornethylenefuorene) . With organolithium compounds a number of dehydrohalogenations, which are formally @-eliminations, actually proceed via deprotonation on the halogenbearing carbon atcm (u-metallation). a-Metallations are the rate-determining steps when ether is used as solvent, but proceed quickly in tetrahydrofuran even at low iemperatures. Compounds of the type >C=C(Li)CI may be prepared by this method and are recognized as intermediates in u-eliminations.

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A Rapid Catalytic Preparation of Sodamide in Liquid Ammonia and Some of its Uses in the Preparation of Acetylenic Materials

Cited by 105 publications

References 0 publications

Improved Alkali Intercalation of Carbonaceous Materials in Ammonia Solution

Improved Alkali Intercalation of Carbonaceous Materials in Ammonia Solution

Platin(0)‐Komplexe mit amino‐substituierten Alkinen: Neue Metallorganische Bausteine für supramolekulare Architekturen und „Kristall‐Engineering”︁

Eliminations from Olefins

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