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Strained rings

The polarization fiinctions are essential in strained ring compounds because they provide the angular flexibility needed to direct the electron density mto the regions between the bonded atoms. [Pg.2172]

For all calculations, the choice of AO basis set must be made carefully, keeping in mind the scaling of the two-electron integral evaluation step and the scaling of the two-electron integral transfonuation step. Of course, basis fiinctions that describe the essence of the states to be studied are essential (e.g. Rydberg or anion states require diffuse functions and strained rings require polarization fiinctions). [Pg.2189]

The following data ( fable 1) for niolcctilcs, including hydrocarbon s, strained ring system s. molecn les with heieroatom s, radicals, and ions conies from a review by Stewart. For most organic molecules,, YM 1 reports heals of formation accurate to within a few kilocalories per rn ol. bor soni e molecules (particularly inorgari ic compoun ds wdth several halogens, such as perch loryl fluoride, even the best sem i-em pineal method fails completely. [Pg.130]

Nucleophilic ring opening of epoxides by ammonia (Section 16 12) The strained ring of an epoxide is opened on nucleo philic attack by ammonia and amines to give 3 ammo alcohols Azide ion also re acts with epoxides the products are p azido alcohols... [Pg.927]

A drawback to the Durham method for the synthesis of polyacetylene is the necessity of elimination of a relatively large molecule during conversion. This can be overcome by the inclusion of strained rings into the precursor polymer stmcture. This technique was developed in the investigation of the ring-opening metathesis polymerization (ROMP) of benzvalene as shown in equation 3 (31). [Pg.35]

The broad conclusion of all these studies is that alkyl radicals are shallow pyramids and that the barrier to inversion of the pyramidal structures is low. Radicals also are able to tolerate some geometric distortion associated with strained ring systems. [Pg.679]

Tbe best conditions for observing S3 are 440 C and lOmmHg when 0-20% of vapour species comprise this deep cbeny-red bent Iriatomic species like ozone, p. 607, it bas a singlet ground slate. Tbe best conditions for Sj are 450 C and 20 mmHg (concentration 20 v ) but tbe structure is still not definitely established and may, in fact be a strained ring, an unbranched diradical chain, or a branched-chain isostructural with SOi(g) (p. 703). [Pg.661]

Epoxides, in contrast to ethers, readily undergo nucleophilic attack, resulting in ring opening and relief of strain. Ring opening proceeds by a different mechanism, and may lead to different products, depending on reaction conditions. [Pg.130]

Other radical reactions not covered in this chapter are mentioned in the chapters that follow. These include additions to systems other than carbon-carbon double bonds [e.g. additions to aromatic systems (Section 3.4.2.2.1) and strained ring systems (Section 4.4.2)], transfer of heteroatoms [eg. chain transfer to disulfides (Section 6.2.2.2) and halocarbons (Section 6.2.2.4)] or groups of atoms [eg. in RAFT polymerization (Section 9.5.3)], and radical-radical reactions involving heteroatom-centered radicals or metal complexes [e g. in inhibition (Sections 3.5.2 and 5.3), NMP (Section 9.3.6) and ATRP (Section 9.4)]. [Pg.11]

Radicals with very polar substituents e.g. trifluoromethyl radical 2), and radicals that arc part of strained ring systems (e.g. cydopropyl radical 3) arc ct-radicals. They have a pyramidal structure and are depicted with the free spin resident in an spJ hybrid orbital. nr-Radicals with appropriate substitution are potentially chiral, however, barriers to inversion are typically low with respect to the activation energy for reaction. [Pg.12]

FIGURE 17. The HOMO in trimethylene sulphide, sulphoxide and sulphone, to be compared with the ones for the strained rings (Figure 16) and for the open-chain derivatives (Figures 14 and 15). [Pg.25]

There is one important case in which SM is not constant for a given group, and that is when the group appears as a member of a strained ring system. In that case, the atomic... [Pg.31]

The strained-ring compound 1,1-dimethyl-l-silacyclobutane (which may be regarded as an olefin of organosilicon chemistry) reacts with diiron nonacarbonyl in benzene at 6°-20°C as shown in Eq. (100) (89). (There is here some analogy with the reactions of transition metal complexes with strained hydrocarbons, which often produce valence tautomerization.) The... [Pg.293]

Carbocation-carbanion zwitterionic intermediates were proposed for the thermal cleavage of several cyclic compounds. In most of these reactions the ionically dissociating bond belongs to one of four strained ring systems, i.e. cyclopropane (13), cyclobutane (14), cyclobutene (15) or norbornadiene (16). The mechanism is distinguished from the formation of a diradical intermediate through homolysis in terms of solvent and substituent effects... [Pg.186]

In order to account for the nonvolatility, infusibility, and limited solubility, Leuchs postulated polymerization of the ground type cyclic compound, as indicated by the subscript x in his formula given above. It is now well established that linear polypeptides are produced on decarboxylation of the N-carboxyanhydrides of a-amino acids, and under favorable conditions the chain length may be fairly large. Leuchs favored the view that strained rings, i.e., those of other than five or six... [Pg.16]

Three-membered strained ring systems constitute an attractive class of molecules as synthetic intermediates [34-36]. Among them the rigid, unsaturated cyclopropenes are the key to selective useful transformations [37,38]... [Pg.143]

When this strained ring opens, this can give rise to polymerisation that can be very dangerous due to exothermicity. Note that it will be very difficult to explain an accident by decomposition leading to the destruction of the molecular structure or polymerisation. [Pg.266]

Aziridine is the only one that has a serious instability risk according to CHETAH. It is due to the presence of a strained ring, which gives an endothermic character to the compound. As its stability should be more or less the same as ethylene oxide, so should be its propensity for polymerisation. [Pg.288]


See other pages where Strained rings is mentioned: [Pg.244]    [Pg.115]    [Pg.117]    [Pg.491]    [Pg.24]    [Pg.400]    [Pg.391]    [Pg.502]    [Pg.79]    [Pg.32]    [Pg.70]    [Pg.6]    [Pg.7]    [Pg.30]    [Pg.225]    [Pg.28]    [Pg.315]    [Pg.329]    [Pg.444]    [Pg.233]    [Pg.45]    [Pg.21]    [Pg.308]    [Pg.208]    [Pg.94]    [Pg.260]    [Pg.323]   
See also in sourсe #XX -- [ Pg.175 ]

See also in sourсe #XX -- [ Pg.36 , Pg.185 , Pg.319 , Pg.320 , Pg.321 , Pg.322 , Pg.323 , Pg.324 , Pg.325 , Pg.326 ]

See also in sourсe #XX -- [ Pg.496 , Pg.498 ]




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1.3- Dioxolanes ring-strain energies

Acid-catalyzed ring strain

Alkanes cyclic, ring strains

Amines cyclic ring strains

And ring strain

Aziridine ring strain

Baeyer ring-strain theory

Bicyclic rings, strain

Carbocyclic compounds ring strain

Carbon coupling constants ring strain

Carbon rings, ring strain

Cationic structures strained ring cations

Conventional ring strain energy

Cope rearrangements ring strain

Copolymers ring-opening polymerization, strained

Cross-ring strain

Cycloalkane ring strain

Cycloalkanes, ring strain

Cyclobutanol, l- synthesis ring strain

Cyclohexane ring strain

Cyclopropane Ring strain energy

Cyclopropane strained ring cations

Cyclopropanone, effect of ring strain reactivity

Cyclopropenes ring strain

Dioxetanes ring strain

Driving Force 2 - Ring Strain

Epoxides ring strain

Four-membered ring compounds strain energy

Heterocyclic compounds ring strain

Highly Strained Ring Systems

Hyperconjugation ring strain

Influence of basicity and ring strain

Large-ring acetylenes strained

Lipoic acid ring strain

Methylenecyclobutane, ring strain

Networks Crosslinked by Strained-Ring Precursors

Nitrate esters from the ring-opening of strained oxygen heterocycles

Nomenclature ring strain

Olefination strained ring systems

Oxirane reactions ring strain

Preparation and Properties of Strained Medium-ring Systems

Quadricyclane strained-ring

ROMP of High and Low Ring-Strain Monomers

Relief of ring strain

Ring Strain and the Structure of Cycloalkanes

Ring compounds strain

Ring strain

Ring strain

Ring strain additivity

Ring strain analysis

Ring strain aziridine reactions

Ring strain correction

Ring strain cyclic

Ring strain cycloalkanes, Table

Ring strain cyclobutane

Ring strain cyclopentane

Ring strain cyclopropane

Ring strain cyclosilanes

Ring strain driving rearrangement

Ring strain energies

Ring strain in cyclopropane

Ring strain in terms of atomic energies

Ring strain in terms of bond energies

Ring strain influence

Ring strain ionic species

Ring strain ketones

Ring strain lactams

Ring strain lactones

Ring strain measurements

Ring strain nonbonded atom interactions

Ring strain oxetane

Ring strain presence

Ring strain reactions

Ring strain relaxation

Ring strain stereochemistry affected

Ring strain, isoxazolidines

Ring strain, metallocenophanes

Ring-closing metathesis strained compounds

Ring-expansion of strained

Ring-opening polymerization strained metallocenophanes

Rings strain and reactivity

Rings strained, functionalize

STRAINED-RING COMPOUNDS

Small rings introduce strain inside the

Small rings introduce strain inside the ring and higher s character outside it

Stability of Cycloalkanes Ring Strain

Strain Energy of the Cyclopropane Ring

Strain in Cycloalkane Rings

Strain in Three-Membered Rings

Strain in medium rings

Strain relaxation, small ring molecules

Strain rings other than

Strain small ring compounds, table

Strain small rings

Strain, in ring systems

Strain, in rings

Strain, in small rings

Strained oxygen heterocycles, ring-opening

Strained ring compounds photochemical cycloaddition

Strained ring compounds preparation

Strained ring compounds synthesis

Strained ring ethers

Strained ring systems

Strained ring-tilted metallocenophanes

Strained ring-tilted metallocenophanes bridge

Strained-ring cyclic compounds

Sulfides cyclic ring strains

Sultones ring strain

Tetrahydropyran ring strain

The Nature of Ring Strain

The Relative Stabilities of Cycloalkanes Ring Strain

Three-membered rings, ring strain

Unsaturated rings, strain

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