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Ring small

For oxaziridines the A-inversion barrier is considerably higher than that for similar aziridines. A-Alkyl-3,3-dialkyloxaziridines are resolvable and absolute configurations have been determined (CHEC 5.08.2.3.1). [Pg.159]

The rotational barriers of A-nitroso-, A-formyl and A-(A,A-dimethylcarbamoyl)-azetidines, compared with those of analogous acyclic amides, suggest that amide conjugation is weaker when the nitrogen is part of an azetidine ring (87KGS912). [Pg.160]

Fully unsaturated seven-membered heterocyclics have alternating bond lengths and are normally in boat conformations. Ring inversion barriers are 42.7 kJ mol-1 for 3-methyl-3ff-azepine and 35.6 kJ mol-1 for 3//-azepin-2-one (CHEC 5.16.2.3). The barriers for oxepin and thiepin are somewhat lower. Annulation can introduce large conformational barriers, to the extent of making possible the resolution into enantiomers of a tribenzoxepin (71CB2923). [Pg.160]

Fully saturated seven-membered heterocycles with one or two heteroatoms are normally in mobile twist-chair conformations (CHEC 5.17.1.1, CHEC 5.18) (B-77SH(2)123). Annulation and the introduction of exocyclic double bonds can have profound effects oxepan-2-one, for example, is in a near chair conformation (67JA5646). [Pg.160]

Minimal interaction between the amine lone pair of electrons and the delocalized tt system of the ring is confirmed by X-ray crystal structures for 6-amino-, 6-dimethylamino-, and 6-moipholino-1,3,5,2,4-trithiadiazepine (36 R1 = H, R2 = NH2, NMej, morpholino) (90CC1315). In each case, the amino group is tetrahedral and rotated out-of-the-plane of the ring such that the nitrogen lone pair is approximately orthogonal to the ir-system. [Pg.160]

Another surprising observation is the considerable stability of [l.l.ljpropellane, first synthesized by Wiberg in 1982. Along with cubane (another very strained but very persistent molecule synthesized by Eaton in 1964), [l.l.l]propellane and tetra(f-butyl)tetrahe-drane illustrate an important concept. Typically, we expect a very strained molecule to be unstable or reactive —requiring very low temperatures or special conditions for characterization—and this is usually the case. However, simply having a very large amount of strain does not guarantee that a molecule will be reactive. The molecule must have a kinet-ically viable path to release the strain. The molecules are unstable, but persistent. Alternatively, we say the molecules are thermodynamically unstable, but kinetically stable. [Pg.125]

Mazieres,., Raymond M. K., Raabe, G., Prodi, A., and MichL ]. (2]Slaffane Rod as a Molecular Rack for Unraveling Conformer Properties Proposed Singlet Excitation Localization Isomerism in anti anti anti- [Pg.126]

Cubanes Starting Materials for the Chemistry of the 1990s and the New Century. Augew. Chcm. hit. Ed. Ettg., 31,1421-1436 (1992). Zhang, M.-X., Eaton, P. E., and Gilardi, R. Hepta- and Octanitrocubanes.  [Pg.126]


Rings have a profound influence on many properties of a molecule small rings introduce. strain into a molecule, aromatic rings dramatically change its physical and chemical properties, rings present particular problems in syntheses, etc. Thus, a knowledge of the I ings contained in a molecule is important in many applications in chemoinformatics. [Pg.53]

The number of possible conformations rises dramatically with increasing ring size. Therefore, large ring systems carmot be handled by the methods applied to small rings. However, in rigid polymacrocyclic structures for example, an overall... [Pg.100]

Review problem 30 This may look rather difficult, but concentrate on the small ring and use the disconnection you know. Suggest a synthesis for TM 299. [Pg.97]

Analysis the small ring will dominate the strategy, and only one disconnection will make the stereochemistry secure. Writing R = n-hexyl ... [Pg.129]

Lactones whose rings are three or four membered (a lactones and p lactones) are very reactive making their isolation difficult Special methods are normally required for the laboratory synthesis of small ring lactones as well as those that contain rings larger than SIX membered... [Pg.815]

CH2— esters 1475-1460 (m-s) 1470-1435 (m-s) Acyclic esters. Frequency increased ca 30 cm for cyclic and small ring systems. [Pg.731]

Substituents on both sides of the double bond are considered separately. Additional vinyl carbons are treated as if they were alkyl carbons. The method is applicable to alicyclic alkenes in small rings carbons are counted twice, i.e., from both sides of the double bond where applicable. The constant in the equation is the chemical shift for ethylene. The effect of other substituent groups is tabulated below. [Pg.792]

The only tme metaphosphate (ring stmcture) of significant commercial interest is sodium trimetaphosphate (STMP), Na P O. Because of the strain inherent in the small ring stmcture, STMP is more reactive toward nucleophiles than chain phosphates. In the presence of NaOH, for example, STMP forms sodium tripolyphosphate. [Pg.338]

Cyclic diesters are often even better substrates forlipases and esterases than acyclic derivatives. Small-ring monoacetates (28, n — 1-3) are obtained in higher yield and ee than the larger derivatives (for 28, n = 4 is only 50%) (43). Hydrolysis of tetrahydrofuran diester results in monoester (29) of ee > 99% (44). [Pg.336]

Small Rings as Substrates for Ring-opening Reactions... [Pg.112]

Dipolarophiles utilized in these cycloadditions leading to five-membered heterocycles contain either double or triple bonds between two carbon atoms, a carbon atom and a heteroatom, or two heteroatoms. These are shown in Scheme 9 listed in approximate order of decreasing activity from left to right. Small rings containing a double bond (either C=C or C=N) are also effective dipolarophiles, but these result in six- and seven-membered ring systems. [Pg.143]

HETEROCYCLIC RING INTERCONVERSIONS 4.03.7.1 Small Rings as Diehophiles or Dipolarophiles... [Pg.153]

Small Rings As Substrates for Ring-opening Reactions 4.03.7.3.1 Three-membered rings... [Pg.155]

Exocyclic unsaturation can stabilize small ring heterocycles. In three-membered rings it is difficult to separate the contributions from increased angle strain and from electronic interactions between the unsaturation and the heteroatom. In four-membered rings such separation has been done 74PMH(6)199, p. 235). The CRSEs change from oxetane... [Pg.3]

Table 8 Stretching Frequencies for Exocyclic Double Bonds on Small Rings ... Table 8 Stretching Frequencies for Exocyclic Double Bonds on Small Rings ...
Radicals of most small and many large heterocycles are known, but their chemistry has not always been explored in depth. The ESR spectra of small ring radicals have been measured and generally found to be in good agreement with theoretical predictions. Table 1 gives some data for three-membered heterocyclics. Noteworthy is the close similarity of the ESR spectra of 1-aziridinyl, 1-azetidinyl and dimethylaminyl (71TL2247). The radicals in the table are all tt-radicals. [Pg.19]

Table 1 ESR Spectra of some Small Ring Nitrogen Radicals... Table 1 ESR Spectra of some Small Ring Nitrogen Radicals...
Fragmentation reactions are particularly common in small rings. Relief of strain and the gain in stability in forming certain common fragments (such as N2, CO2), as felt in the... [Pg.19]

Ring expansion of small rings is once again favored by ring strain, and many 3 5 conversions are known. Four-membered rings can expand to five- or six-membered ones. Examples are given in Scheme 13. [Pg.22]

Surprisingly little is known about the attack of radicals on small and large heterocycles. Hydrogen abstraction from the heteroatom of small rings leads to ring opening, and in the... [Pg.25]

Heterocyclics of all sizes, as long as they are unsaturated, can serve as dipolarophiles and add to external 1,3-dipoles. Examples involving small rings are not numerous. Thiirene oxides add 1,3-dipoles, such as di azomethane, with subsequent loss of the sulfur moiety (Section 5.06.3.8). As one would expect, unsaturated large heterocyclics readily provide the two-atom component for 1,3-dipolar cycloadditions. Examples are found in the monograph chapters, such as those on azepines and thiepines (Sections 5.16.3.8.1 and 5.17.2.4.4). [Pg.28]

Synthesis of heterocycles by forming C—X bonds by radical reactions is not a generally applicable method, and seems not to be useful for making small rings. However, the attack of thiol radicals on double bonds can be a practical synthetic route, such as in the conversion of 1-hexene-7-thiol to thiepane (Section 5.17.3.3.1). [Pg.34]

The conversion of small rings to smaller ones, without loss, is not common. 3-Chloroazetidine isomerizes reversibly to 2-chloromethylaziridine (Section 5.09.2.2.5). Flash vacuum pyrolysis can convert isoxazoles to azirines (Section 5.04.4.3). More common is the isomerization of medium-sized, i.e. five- or six-membered rings, e.g. certain succinimides (Scheme 23) (81JOC27) to azetidinediones, or bicyclic 1,2-dioxetanes to bis-oxiranes (Section 5.05.4.3.2). [Pg.42]


See other pages where Ring small is mentioned: [Pg.101]    [Pg.326]    [Pg.339]    [Pg.88]    [Pg.72]    [Pg.313]    [Pg.114]    [Pg.312]    [Pg.299]    [Pg.97]    [Pg.72]    [Pg.49]    [Pg.112]    [Pg.112]    [Pg.154]    [Pg.3]    [Pg.6]    [Pg.11]    [Pg.12]    [Pg.12]    [Pg.19]    [Pg.23]    [Pg.24]    [Pg.36]    [Pg.41]    [Pg.45]    [Pg.47]   
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See also in sourсe #XX -- [ Pg.97 , Pg.98 , Pg.99 , Pg.305 , Pg.306 , Pg.307 , Pg.326 , Pg.327 , Pg.328 , Pg.329 , Pg.330 , Pg.345 , Pg.346 , Pg.347 , Pg.348 , Pg.349 ]

See also in sourсe #XX -- [ Pg.163 ]

See also in sourсe #XX -- [ Pg.163 ]




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Alkynes and small rings

And small rings

Carbenes small rings, generation

Cyclization reactions small ring compounds

Cycloaddition reactions small ring compounds

Cycloadditions small ring compounds

Cycloalkane rings Small

Cycloalkanes small-ring

Cyclobutanes small ring compounds

Cyclopropanes small ring compounds

Cyclopropenes small ring compounds

Electronic spectra of small-ring heterocyclic compounds

Formation of Small Rings

Gas-phase pyrolysis of small-ring

Gas-phase pyrolysis of small-ring hydrocarbons

Generation of dipolar intermediates from small rings

Hydrocarbons, small-ring, gas-phase

Hydrocarbons, small-ring, gas-phase pyrolysis

Hydrogenation of small alicyclic rings

Intramolecular nucleophilic substitution small rings

Matrix Photochemistry of Small Ring Compounds

Matrix photochemistry, small ring

Matrix photochemistry, small ring compounds

Metal-catalyzed Cycloaddition of Small Ring Compounds

Metallomacrocycles small ring

NMR spectra of alkynes and small rings

Nitrenes small rings

Nuclear magnetic resonance small and large rings

Nucleophile effects small rings

Nucleophilic addition small rings

Nucleophilic aliphatic small rings

Olefins small ring

Organosilane Reduction of Small-Ring Compounds

Other Small Ring Intermediates

Photolysis small ring compounds

Propellanes small-ring

Propellanes, small ring structures

Reactions on small rings

Reactivity of 1-Functionalized-l-Metallo. Small Ring Compounds

Reactivity of Small and Large Rings

Rearrangements small rings

Ring opening small cycles

Rings small, medium and large, definitions

STRUCTURE OF SMALL HETEROCYCLIC RINGS

Small Rings Cyclopropane and Cyclobutane

Small Rings and Conjugated Systems

Small Rings by Azide Chemistry

Small ceramic rings

Small ring compounds

Small ring compounds metal-catalyzed

Small ring compounds, table

Small ring nitrogen heterocycles

Small ring synthesis

Small rings introduce strain inside the

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

Small rings, definition

Small-Ring Organosilicon Compounds

Small-membered ring compounds

Small-ring Compounds of Sulphur and Selenium

Small-ring stabilization

Small-sized ring

Stereochemistry small rings

Strain relaxation, small ring molecules

Strain small ring compounds, table

Strain small rings

Strain, in small rings

Structure of Small and Large Rings

Substituent effects small rings

Theoretical studies small ring substitution

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