Unsaturated materials

Sulfur monochloride [10025-67-9] S2CI2, and sulfur dichloride,SCl2, react with unsaturated materials, forming products that are cross-linked by sulfur but which also contain chlorine (eq. 7) (10). 

Carbonyl-containing and unsaturated materials are removed by treatment with sodium borohydride (227,228) and boric acid (229). Other methods used to remove carbonyl impurities include treatment with hydroxyl amine hydrochloride, potassium permanganate, or A/-hydroxyben2enesulfonamide (229). 

Olefins are the basic building blocks for many chemical syntheses. These unsaturated materials enter into polymers, rubbers, and plastics, and react to form a wide variety of chemical compounds such as alcohols, amines, chlorides and oxides. 

Scherer, O. J. et al., Angew. Chem. (Intern. Ed.), 1967, 6, 701-702 The crude highly unsaturated material decomposes explosively if stored in a refrigerator or on attempted distillation under water-pump vacuum (moisture ). However, it is distillable under oil-pump vacuum and is then stable in refrigerated storage. It decomposes explosively with traces of water or ethanol, and polymerises in daylight at ambient temperature. 

The rate constants for these reactions are outlined in Table 1, and in all cases indicate that the tin and germanium radicals are less reactive than the silicon analogue. The rate constants for the addition of these radicals with other unsaturated materials are also presented. 

The degree of unsaturation of a fatty chain is classified by the iodine value (I. V.), defined as the weight of iodine that can react with 100 g of unsaturated material. 

The unsaturated molecule Y may be carbon monoxide, an olefin, a conjugated diene, an acetylene, a carbonyl compound, various unsaturated carbon-nitrogen compounds, or probably any of several other unsaturated materials. The reactive part of the covalent metal compound is usually a metal-hydrogen, metal-carbon, metal-oxygen, metal-halogen, metal-nitrogen, or metal-metal group. This reaction... 

Reactions of Alkenes and Alkynes in Presence of Metal Carbonyls. Metal carbonyls—e.g., Ni(CO)4, Fe(CO)5, and Co2(CO)s—and hydrocarbonyls— HCO(CO)4 and H2Fe(CO)4—act as catalysts for the transformation of simple unsaturated materials into a wide variety of larger molecules. Perhaps the simplest example is that of hydroformylation (Equation 7). Reppe chemistry... 

The unsaturated zone, where most of the low-level waste is buried, could probably be used for high-level waste after cooling but it does not lend itself to the regional approach to defining permeability. Additionally, the laboratory methods of evaluating permeability of unsaturated material are extremely difficult to perform consistently. However, an air permeability technique that may prove useful in evaluating the zone between the surface and the water table was developed by Weeks W. The technique uses normal barometric fluctuations measured at different depths in the formation to determine permeability to air which can be used to determine permeability to water. 

However, the ratios of the unsaturated materials to the saturated materials and of the ketones to the alcohols (Table I) indicate that the yields of unsaturated materials are higher than those of saturated products, especially cyclohexenol. [The excess alcohol might come from 2ROO - 2RO- + 02 however, its importance in the gas phase is unknown.] It was suggested from the above that some cyclohexenol and possibly cyclo-hexenone may be formed from cyclohexenyl hydroperoxide which is produced from chain reactions initiated by the cyclohexyl peroxy radical and cyclohexenyl peroxy radical as shown below. 

It is perhaps unsurprising that the role of phosphane ligands in group 10 poly(pyrazolyl)borate complexes can often be summarized as "spectator-ial," and in many instances is incidental in respect of chemistry. Indeed, the dominant utility of these ligands is as donors with which to trap or stabilize coordinately unsaturated materials. 

If the radical formed is not stable or stabilized at the electrode, it is instantly reduced further. The carbanion thus produced may either react with hydrogen ions or with the reducible, unsaturated material according to Scheme 3. 

The LPG stream produced by pyrolysis cracking contains all possible C3 and C4 molecules. As well as olefins, prominent are highly unsaturated materials such as acetylenes and dienes. 

C) Tests for Unsaturation. Determine which of the following hydrocarbons are saturated and which are unsaturated or contain unsaturated material. Use any of the above tests that seem appropriate. 

It follows from this discussion that all solvents and monomers used must be carefully purified. Hydrocarbons should be stirred over sulphuric acid for many days and ethers refluxed over sodium—potassium alloy or sodium fluorenone before fractionation. Traces of unsaturated materials in aliphatic hydrocarbons can be removed by silica gel. After fractionation, a preliminary drying over calcium hydride can be followed by storage over sodium—potassium alloy for ethers, or a treatment with butyllithium or similar non-volatile reactive organometallic reagent for hydrocarbons. Monomers cannot be treated quite so drastically, but fractionation followed by a pre-polymerization in vacuum over butyl-... 

Epoxides may be generated as reactive intermediates when unsaturated materials are treated with BPs/trifluoroperacetic acid, a powerful oxidation/rearrangement mixture developed by Hart. ° The products from numerous alkenes and aromatic substrates, to the extent that comparisons can be made, are those expected from epoxide/carbenium ion rearrangements. 

To a solution of 1.94 grams of crystalline cannabidiol in 35 cc. of cyclohexane (free from unsaturated material) was added one drop of 100% sulfuric acid. The mixture was refluxed for one hour, at the end of which time the alkaline Beam test was negative. The solution was decanted from the sulfuric acid, washed twice with aqueous 5% bicarbonate solution and twice with water, and evaporated. The residue was distilled under reduced pressure. Three fractions were collected, B. P. 165-170° (0.1 mm.),[a]29 D—259° to—269°. Rotation.—0.0381 gram made up to 5 cc. with acetone at 29° gave [a] D—210° 1, 1 [a]29 D—264°. 

The saturated zone is formed by porous material in which all the pore spaces are filled with water. The water table is defined as the depth at which pore water pressure equals atmospheric pressure. If a hole is dug down to the saturated zone, the location of the water table can be easily determined it is at the depth to which water accumulates in the hole. In coarse porous material, the location of the water table itself very nearly approximates the transition between saturated and unsaturated material in a fine-textured porous material, enough water may move upward by capillarity to cause complete saturation of a measurable thickness above the water table (the capillary fringe). 

The epoxidation of unsaturated materials is the most commonly used reaction of dioxiranes. The reaction, whether carried out in situ or using the solution method, gives high yields of epoxides, usually in rapid reactions. The isolated dioxirane method is particularly useful in cases where oxidation products are sensitive to the acidic conditions of the most commonly used epoxidation reagents or the basic conditions of the in situ method. Use of the isolated dioxirane permits reaction under neutral conditions so that labile epoxides are conveniently prepared. When the desired epoxide is sensitive to moisture, the dioxirane solution can be dried with molecular sieves for use in such epoxidations. The epoxidation of water-insoluble alkenes with the in situ method requires the use of a phase-transfer catalyst, but the reaction still proceeds in high yields. Dioxiranes, in situ generated... 

Dialkyl peroxydicarbonates, R0C(=0)00C(=0)0R, are employed as polymerization initiation catalysts the doubly unsaturated material diethylene glycol bis(allyl carbonate),... 

Phosgene does not react with ethanoic acid at normal temperatures, but ethanoyl chloride is produced according to Equation (10.22) when the reactants are combined in a Carius tube at 120 C [1080]. Long-chain acids, such as CH 3(CH j) ,COOH (n = 10, 14 or 16) have been treated in the molten state at 150 "C, and the unsaturated material, CH3(CHj) CH=CH(CHj)jCOOH, behaves similarly i.e. according to Equation (10.22) [1658]. 

Use of beta zeolite catalyst does not require the benzene feed to be clay treated prior to use in alkylation service. Some of the unsaturated material in the benzene can lead to the formation in the alkylation reactors of polycyclic-aromatic material which will get preferentially trapped in some zeolites having relatively small-sized pores. This can lead to increased deactivation rates in such small-pore zeolites. Beta zeolite s large pore structure makes it possible to more easily handle this polycyclic-aromatic material and as a result does not require further treatment of the benzene feed to remove unsaturated material. In addition, alpha-methylstyrene (AMS) is produced by alkylation of benzene with methylacetylene or propadiene. Some of the AMS alkylates with benzene, forming diphenyl-propane, a heavy aromatic that leaves the unit with the DIPB column bottoms. 

The purpose of hydrocracking is to convert high-boiling feedstocks to lower boiling products by cracking the hydrocarbons in the feed and hydrogenating the aromatic and unsaturated materials in the product streams.f ... 

It is instructive to calculate ASO - H20(%o), which is the difference between the 5 0 values of sol and H2O in mine water (Fig. 12.22). In the absence of isotope fractionation and with Fe as the oxidant, a zero difference would be expected. Taylor et al. (1984b) propose that Fe dominates pyrite oxidation in submersed environments. For such conditions ASO - H20(%o) values exceed zero due to isotope fractionation, ranging from about 4 to 6 in sterile systems to about 11 in the presence of T. ferrooxidans. Fractionation is caused by the greater reactivity of light 0 than heavy 0, with thus favored in product sulfate. Bacterial activity (in this case T. ferrooxidans) causes more fractionation than takes place in the abiotic oxidation reaction. ASO - H20(% ) values range up to about 18 when O2 is the chief oxidant in the presence of bacteria. S uch conditions are expected in aerated streams and in shallow unsaturated materials (Taylor et al. 1984a, 1984b). 

Poutsma, M. L., Chlorination Studies of Unsaturated Materials in Nonpolar Media. 3. Competition between Ionic and Free radical Reactions During Chlorination of Isomeric Butenes and Allyl Chloride, J. Am. Chem. Soc. 1965, 87, 2172 2183. 

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