Double bonds, formulation

It is an air sensitive but reasonably thermally stable solid with a slightly bent, trans structure (0 = 18°). In most other disilenes the 0 angle is smaller (ca. 0°) and the Si atoms and the atoms to which they are bonded are nearly coplanar. The typical Si=Si bond (2.15 0.01 A) is 10% shorter than a typical Si—Si bond. Other factors consistent with double bond formulation for disilenes are the deshielded 29Si nmr chemical shifts and large / (SiSi) coupling constants. 

Acetic acid treatment of the transition metal Ge(IV) hydride salt Kb/5-C5H5Mn(CO)2GeH3] yields a red product, b/5-C5H5Mn (CO)2]2Ge, which contains a linear Mn-Ge-Mn system in which the germanium atom occupies a special position with equal Ge-Mn distances of 2.204 A. Solution infrared spectra show four v(CO) stretching absorptions instead of the two expected from the cen-trosymmetric structure in the solid state, implying free rotation about the Ge-Mn bonds. Simple application of the rare-gas rule would favor a double-bonded formulation containing Ge(IV), but a molecular-orbital... 

Anionic halide dimers of Nb(III) are prepared in quartz ampules at 600-700°C from CsX and NbsXs (X = Cl, Br, I)T The [Nb2Br9] ion displays a confacial bioctahedral geometry (Nb-Nb 277 pm) and is paramagnetic in accord with a double-bond formulation in which only two electrons occupy degenerate 7t-bonding orbitals. No description of analogous Ta(III) anions is available. 

Since double bonds are no longer present, these compounds are more stable than the corresponding furan derivatives. Tetrahydrofurfuryl alcohol—ethylene oxide adducts [31692-85-0] are also usehil solvents for paint stripping formulations (136,141,143). 2-Methylfuran is a good solvent, but... 

An ingenious approach to the synthesis of steroids incorporating a tropone A ring has been developed by Birch and co-workers. Addition of dibromocarbene to 3-methoxyestra-2,5(10)-dien-17-one 17-ethylene ketal (42) gives a monodibromocarbene adduct formulated as (43) accompanied by a minor amount of a bisadduct. This confirms earlier observations that electrophilic halocarbenes add mainly to 2,3- or 2,5-dihydroanisoles at the double bond bearing the methoxyl group. 

Kekule structure (Section 11.2) Structural formula for an aromatic compound that satisfies the customary rules of bonding and is usually characterized by a pattern of alternating single and double bonds. There are two Kekule formulations for benzene ... 

The general rule has been formulated (P) that the less substituted enamine is formed from unsymmetrical ketones such as the 2-alkylcyclohexanones. In enamine 21 the R, group and the N-alkyl groups would interfere with one another if overlap is to be maintained between the nitrogen unshared electrons and the double bond. There would be less repulsion if the isomeric enamine (22) were formed. 2-Phenylcyclohexanone and pyrrolidine with p-toluenesulfonic acid as catalyst in refluxing benzene gave enamine... 

As pointed out in the introduction, if one of the substituents on the nitrogen atom is a hydrogen atom, tautomeric equilibrium between enamino and imino forms strongly favors the latter form 18,140,141). According to physiochemical measurements, the occurrence of simply substituted /1 -pyrrolines and zl -piperideines is very improbable. The formulation of this type of compound with a double bond in the position (used mainly by early authors) was of formal meaning only, having no experimental evidence (142-144). 

Tertiary pyrrolines (49, = 1) and piperideines (49, = 2) (if R = H and the enamine can exist in the monomeric form or if R = aryl) evidently possess an endocyclic -double bond (79,155,156). The stretching frequency of the double bond can be lowered to 1620-1635 cm by conjugation with an aromatic substituent. The double bond of an analogous compound with aliphatic substituents in position 2 may occupy either the endo or the exo position. Lukes and co-workers (157) have shown that the majority of the five-membered-ring compounds, traditionally formulated with the double bond in a position, possess the structure of 2-alkylidene derivatives (50) with an exocyclic double bond, infrared absorption at 1627 cm . Only the 1,2-dimethyl derivative (51) is actually a J -pyrroline, absorbing at 1632 cm . For comparison, l,3,3-trimethyl-2-methylene pyrrolidine (52) with an unambiguous exocyclic double bond has been prepared (54). 

A final statement on the mechanism of the diaziridine formation cannot yet be made. The obvious formulation [Eq. (36) ] as a reaction of the CN double bond with the imen 39 (with an electron sextet) is almost certainly excluded. The formation of 39 as an intermediate has been jiroposed for the Raschig hydrazine synthesis, but has been disjmted. The following facts are against a diaziridine formation corresjionding to Eq. (36) ... 

The hydrazone structure 40 can be eliminated at once many examples of this class of compounds are known and their properties are completely different from the diaziridines. For example, 3,3-dimethyldiaziridine has a heat of combustion of about 35 kcal higher than the isomeric acetone hydrazone. Further pairs of isomers of diaziridines and hydrazones are known. The spectrum eliminates both the hydrazone structure and the betaine structure 41. The diaziridines do not absorb in the UV range. In the infrared spectrum, absorption is completely absent in the double-bond region. - The NMR spectrum of 3,3-dimethyldiaziridine is in agreement with a formulation that has two equivalent iV-protons. ... 

The addition reaction of the methylene to the carbon-carbon double bond is formulated as a one-step mechanism, where both new carbon-carbon bonds are formed simultaneously in a transition state of a structure like 5 ... 

Several generalities can be formulated regarding selective reduction of polyolefins. Usually the least hindered double bond is hydrogenated pre ferentially (123), and, with steric hindrance about equal, the most strained bond will be reduced first. Exocyclic olefins are reduced more easily than those in the ring (R)-(+ )-Limonene, 190 g, was shaken with W-4 Raney nickel (12 g) under hydrogen at atmospheric pressure. After 31.9 1 of hydrogen had been absorbed, the solution was filtered. Essentially, pure (R)-( -i- )-carvomenthene was obtained in 96% yield (58). 

According to Zaitsev s rule, formulated in 1875 by the Russian chemist Alexander Zaitsev, base-induced elimination reactions generally (although not always) give the more stable alkene product—that is, the alkene with more alkyl substituents on the double-bond carbons. In the following two cases, for example, the more highly substituted alkene product predominates. 

Muller et al. [80] described the use of IOS surfactants together with the sulfonate of a C12-C24 unsaturated fatty acid containing one to six double bonds in shampoo formulations they combine good detergency with good foam properties and mildness to the skin. 

The determination of values of interatomic distances in molecules has been found to provide much information regarding electronic structure, especially in the case of substances which resonate among two or more valence-bond structures. The interpretation of interatomic distances in terms of the types of bonds involved is made with use of an empirical function formulated originally for single bond-double bond resonance of the carbon-carbon bond.1 There are given in this... 

Based on these considerations, Croft prepared six formulations containing various combinations of NBR and NBR/PVC with CR and SBR and measured their oil, heat and ozone resistance, physical properties, and adhesion characteristics. Whereas the physicals are satisfactory for aU compounds, formulations based on NBR, NBR/PVC with CR performed better on heat and oil aging than the compounds containing SBR as shown in Tables 11.6 and 11.7. However, the adhesion is better with the latter compounds. It has been suggested that cuprous sulfide formed on the wire surface interacts with the double bond in SBR to provide the improvement in adhesion. 

There are over 400 different commercial alkyd resin formulations based on phthalic anhydride used in the coatings business. Alkyd resins for paints are made by reacting phthalic anhydride with a poly-alcohol (usually from naturally occurring sources rather than synthetic) that contains unreacted double bonds. The paint dries by the resin crosslinking through reaction of the double bonds under the influence of oxygen in the air. 

The four-membered ring of 66 [Li (dme)3] was perfectly planar with two pairs of distinctly different skeletal Ge-Ge bonds of 2.5116(6) and 2.3679(6) A the former is typical for the Ge-Ge single bonds, whereas the latter is close to the valnes of Ge=Ge double bonds. Such crystallographic features led to the formulation of the allylic-type strncture of 66 , in which the negative charge is delocalized over the Gej fragment of the four-membered ring. 

The reactivity order of alkenes is that expected for attack by an electrophilic reagent. Reactivity increases with the number of alkyl substituents.163 Terminal alkenes are relatively inert. The reaction has a low AHl and relative reactivity is dominated by entropic factors.164 Steric effects govern the direction of approach of the oxygen, so the hydroperoxy group is usually introduced on the less hindered face of the double bond. A key mechanistic issue in singlet oxygen oxidations is whether it is a concerted process or involves an intermediate formulated as a pcrcpoxide. Most of the available evidence points to the perepoxide mechanism.165... 

Addition of carbethoxynitrenes to olefinic double bonds occurs readily. Addition of both the singlet and the triplet species can take place, the former stereospecifically, the latter not 49>. Additions of sulphonyl nitrenes to double bonds have not been demonstrated except in two instances in which metals were present. The reason is that either addition of the starting sulphonyl azide to the double bond occurs to give a triazoline that loses nitrogen and yields the same aziridine as would have been obtained by the direct addition of the nitrene to the olefin, or the double bond participates in the nitrogen elimination and a free nitrene is never involved 68>. The copper-catalyzed decomposition of benzenesulphonyl azide in cyclohexene did give the aziridine 56 (15%), which was formulated as an attack by the sulphonyl nitrene-copper complex on the double bond 24>. 

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