Olefinic adds

Olefins add anhydrous acetic acid to give esters, usually of secondary or tertiary alcohols propjiene [115-07-1] yields isopropyl acetate [108-21-4], isobutjiene [115-11-7] gives tert-huty acetate [540-88-5]. Minute amounts of water inhibit the reaction. Unsaturated esters can be prepared by a combined oxidative esterification over a platinum group metal catalyst. Eor example, ethylene-air-acetic acid passed over a palladium—Hthium acetate catalyst yields vinyl acetate. 

The VP Operations-Olefins adds no value to the process, but is simply acting as a post-box. ... 

On the other hand, Michael-acceptor olefins add to the sulfoxylate stage from dithionite, yielding a sulfinate intermediate which yields, according to the reaction... 

The procedure is illustrative of a general method of ethylating amines, wherein one reacts the amine with ethylene using an alkali-metal salt of the amine as catalyst.2 Di- -butylamine and -hexylamine have been thus ethylated at 130-160°, aniline, o-toluidine, and N-methylaniline at 240-275°. In general, higher olefins add to amines only sluggishly.2... 

Carboxylic acids containing triple bonds are converted to cis olefinic adds by... 

Explain why cis olefins add 1,3-dipoles more slowly than trans olefins, despite the fact that the cis ground states are higher in energy. 

Many reactants in organic chemistry can exist in the form of two or more isomers that give rise to different products. The most typical examples are reactions in which an olefin adds water, halogen, or any compound other than hydrogen under conditions that also promote migration of the double bond. Many reactions of industrial importance belong to this class. 

Photooxidation experiments with other small olefins add strong support to the assignment of the visible absorption of hydrocarbon 02 complexes in zeolites as charge-transfer absorptions [19,20]. For example, the onset of the absorption tail (and the photolysis threshold) shifts linearly to higher energies with increasing ionization potential of the olefin. We have also found that, as expected, the optical absorption onset is sensitive to the magnitude of the electrostatic field. For example, the increase of the electrostatic field upon substitution of Na by Ba is accompanied by a red shift of the 2-butene 02 absorption onset of 100 nm (4000 cm-1) [14]. 

Keefer measured the solubility of cuprous chloride in solutions of various unsaturated alcohols S7> and unsaturated carboxylic acids 58), from which they were able to calculate the formation constants for the species H2MCuC1 and H2MCu2+, although HM-CuQ and HMCu were sometimes considered (H2M is a dibasic olefinic add). By comparison of the solubility of silver bromate in aqueous solutions of unsatured alcohols, it was shown that the cuprous complexes were considerably more stable than the corresponding silver(I) complexes. Whether this is generally true, as has been suggested S9) is open to speculation. 

Seoondary and etheric secondary olefine adds. Halations of the laotic to the acetic Beries of adds Delations af the lactic to the acrylic series of adds... 

Hus series is dirided into normal, secondary, and olefine adds. In the normal arid n> 0 in the secondary it must be a positive integer. 

Olefins add hydrogen fluoride very readily, but polymerization of the olefins also occurs as a side reaction. Traces of acid and water, or temperatures of about 70°, lead to loss of HF from the alkyl fluorides produced. Preparative importance attaches to addition of HF to chlorinated olefins, whose tendency to polymerize in presence of HF is less the more Cl atoms are attached to the doubly bonded carbon atoms. HF adds readily to olefins with unsymmetrical halogen substitution, such as CH2=CHX, RCH=CX2, or RCX=CH2, but with greater difficulty when halogen is attached to both the doubly bonded carbon atoms. BF3, which assists removal of H+ from HF by complex formation, accelerates the reaction but also the exchange of halogen for fluorine and the resin formation by polymerization that occur as parallel reactions.169... 

Sodium hydrogen sulfite can be added to olefins under pressure but also at a useful rate at atmospheric pressure in the presence of tertiary peroxides.60 The course of the addition depends considerably on the reaction conditions and on the nature of the solvent. Kharasch and his co-workers61 have reviewed the applicability of this reaction in relation to the nature of the olefin and the reaction conditions. a-Nitro olefins add sodium hydrogen sulfite even in aqueous solution at 0°, yielding l-nitroalkane-2-sulfonates. 

Figure 2 represents the hydride mechanism in which H2 adds before the olefin. Sometimes the olefin adds first (the olefin mechanism) as is found for [Rh(dpe)(CH30H)2]BF4 (10). 

In these equations, the first three steps of the probable mechanism (see p. 5) have been condensed into the first step. It is not likely that the olefin adds pirectly to hydrotetracarbonyl. 

Carbocations possess a high reactivity and rapidly enter the following reactions abstract a proton to be transformed into olefin, add to a negative ion (R + XT RX), add to a molecule at the heteroatom with a lone election pair (R + HQR RR OH"), add to a molecule with the double bond (R" + CH2=CHX RCH2 C HX), and add to the aromatic ring (R + RCsH ). Some of these reactions very... 

Strained olefins add to the dithiole-thione (375) to give rearranged products thus norbornadiene affords (376). l,2-Benzodithiole-3-thione (377) and cyclo-pentene form the photoadduct (378). ... 

---