Saturated Aliphatic Halides

Neither the palladium nor nickel catalyst described will promote the carbonylation of saturated aliphatic halides as noted above. However, this reaction can be catalyzed with cobalt (17) or iron (77) and probably with manganese (18) carbonyl anion salts. These carbonyl anions are strongly nucleophilic species and readily displace halide or other good leaving groups from primary or secondary positions giving alkyl metal carbonyl complexes. 

The carboalkoxylation of saturated aliphatic halides may give mixtures of isomeric products if carried out above about 75°, at least with tetra-carbonylcobalt anion as catalyst. Isomerization occurs because the intermediate alkylcobalt complex isomerizes competitively with the carbonylation at the higher temperatures. The isomerization probably involves stepwise loss of carbon monoxides to the tricarbonylalkylcobalt(I) stage. This complex then may reversibly rearrange by a hydride elimination to a hydride-olefin-71 complex. The hydride may also add back in the reverse direction and produce an isomeric alkyl. Subsequent readdition of carbon monoxides and alcoholysis would produce isomerized ester ... 

Of all the alkylating reagents used, saturated aliphatic halides are the most prone to react with the nitrogen atom and give a quaternary ammonium salt. Reactive halides of the allyl type, propargyl bromide,... 

Heterocyclic Sulfur Compounds with Two or More Rings Hexachlorobenzene under Ring-Substituted Aromatics Hexachlorobutadiene under Unsaturated Alkyl Halides Hexachlorocyclohexane Lindane under Saturated Alkyl Halides Hexachlorocyclopentadiene under Unsaturated Alkyl Halides Hexachloroethane under Saturated Alkyl Halides Hexadecane under Alkanes and Cyclic Alkanes Hexafluoroethane under Saturated Alkyl Halides Hexamethyldisihzane under Silicon Compounds—Other Significant Hexanes under Alkanes and Cyclic Alkanes Hexylamine under Primary Aliphatic Amines and Diamines... 

RDX, Cyclonite, Hexahydro-l,3,5-trinitro-l,3,5-triazine under Secondary Aliphatic Amines Ring-Substituted Aromatics Saturated Alkyl Halides Secondary Alcohols... 

The lower members of the homologous series of 1. Alcohols 2. Aldehydes 3. Ketones 4. Acids 5. Esters 6. Phenols 7. Anhydrides 8. Amines 9. Nitriles 10. Polyhydroxy phenols 1. Polybasic acids and hydro-oxy acids. 2. Glycols, poly-hydric alcohols, polyhydroxy aldehydes and ketones (sugars) 3. Some amides, ammo acids, di-and polyamino compounds, amino alcohols 4. Sulphonic acids 5. Sulphinic acids 6. Salts 1. Acids 2. Phenols 3. Imides 4. Some primary and secondary nitro compounds oximes 5. Mercaptans and thiophenols 6. Sulphonic acids, sulphinic acids, sulphuric acids, and sul-phonamides 7. Some diketones and (3-keto esters 1. Primary amines 2. Secondary aliphatic and aryl-alkyl amines 3. Aliphatic and some aryl-alkyl tertiary amines 4. Hydrazines 1. Unsaturated hydrocarbons 2. Some poly-alkylated aromatic hydrocarbons 3. Alcohols 4. Aldehydes 5. Ketones 6. Esters 7. Anhydrides 8. Ethers and acetals 9. Lactones 10. Acyl halides 1. Saturated aliphatic hydrocarbons Cyclic paraffin hydrocarbons 3. Aromatic hydrocarbons 4. Halogen derivatives of 1, 2 and 3 5. Diaryl ethers 1. Nitro compounds (tertiary) 2. Amides and derivatives of aldehydes and ketones 3. Nitriles 4. Negatively substituted amines 5. Nitroso, azo, hy-drazo, and other intermediate reduction products of nitro com-pounds 6. Sulphones, sul-phonamides of secondary amines, sulphides, sulphates and other Sulphur compounds... 

Carbonyl compounds will be taken in this chapter to mean any organic compound that contains at least one carbon-oxygen double bond where we limit the substitution to only saturated aliphatic, saturated alicyclic and aryl hydrocarbyl groups. Carbonyl compounds with a variety of unsaturated substituents have earlier been discussed within the context of enones4. Non-hydrocarbyl substituents, X , may be directly attached to the carbonyl and elsewhere in the molecule. The first type of species, RCOX, is alternatively identified as acyl derivatives such as carboxylic acids and their esters, halides and amides and have already been discussed in a recent Patai thermochemistry... 

The reaction of ylides with saturated aliphatic alkyl halides (like methyl iodide, ethyl iodide etc.) usually stops at the stage of the alkylated salt because the +/ effect of the aliphatic substituent causes the resulting salt to be a weaker acid than the conjugated salt of the original ylide (which would result in the course of a transylidation reaction). However since partial transylidation also occurs between al-kylidenephosphoranes and phosphonium salts with equal or not very different base and acid strength, mixtures may result from Ae reaction with saturated aliphatic alkyl halides. At this point it should be mentioned that the synthesis of dialkylated ylides via the salt method is also difficult since the preparation of the necessary phosphonium salt is accompanied by -elimination. The successful synthesis of dialkylated ylides may be achieved by fluoride ion induced desilylation of a-trimethylsilylphosphonium salts (see equation 18). There is no doubt about the course of ylide alkylation in cases where the inductive effect of the new substituent leads to complete transylidation (e.g. equation 54). ... 

Activation of carboxylic acids by phosphoms acid halides in the form of different derivatives (3-7) has been used extensively in more recent years. These methods have been tested not only for saturated aliphatic or aromatic carboxylic acids but also for functionalized derivatives. In Table 6 some examples are collected where (3) and (4) were applied successfully. The reactions are carried out at room temperature in acetone or dichloromethane by treatment of the carboxylic acid with 1 equiv. of triethylamine or A -ethylpiperidine and 0.5 equiv. of the reagent (equation 25). The anhydrides are either collected by filtration or recovered by evaporation of the solvent after washing with water. 

Saturated Aliphatic Compounds Containing Heteroatoms. A great variety of organic matter falls in this classification—for example, alcohols, ethers, mercaptans, amines, and halides. Two types of simple cleavage reactions may occur that are initiated or directed by the presence of the heteroatom (O, S, N, X, etc.), as exemplified by Equations 16.18 and 16.19 for ethyl ether. Heteroatoms that can stabilize the positive... 

Preparation.—From Alcohols or other Halides. Factors affecting the formation of isomerically and optically pure alkyl halides from saturated aliphatic alcohols have been discussed by Hudson and co-workers. - Reactions with thionyl chloride give reduced amounts of rearrangement products if pyridine hydrochloride is added, and isomerically pure chlorides RCl from almost all alcohols ROH if HMPT or DMF is the solvent. In the latter medium (58) is a presumed intermediate, as is the case in the reaction of alcohols with Vilsmeier reagents (59, X = Cl or Br). Such species produce halides via inversion of configuration from secondary alcohols, presumably according to Scheme 24. In the related reaction of PCI3 with unhindered primary alcohols in DMF to produce alkyl... 

If it is desired to compare bromobenzene with a halide of the aliphatic series, the saturated ethyl bromide must naturally not be chosen... 

Further increment rules for the calculation of 13C shieldings in various types of saturated and unsaturated compounds may be found elsewhere (11). In a totally mathematical approach, Wiberg and co-workers (407,408) analyzed data for 18 sets of aliphatic and alicyclic halides (X = F, Cl, Br, or I) by means of factor analysis. They found that three parameter terms suffice to correlate all the shielding data ... 

Classical organic chemistry provides a wide variety of potential analytes for electron ionization, the only limitation being that the analyte should be accessible to evaporation or sublimation without significant thermal decomposition. These requirements are usually met by saturated and unsaturated aliphatic and aromatic hydrocarbons and their derivatives such as halides, ethers, acids, esters, amines, amides etc. Heterocycles generally yield useful El spectra, and flavones, steroids, terpenes and comparable compounds can successfully be analyzed by El, too. Therefore, El represents the standard method for such kind of samples. 

Chromium(II) sulfate is a versatile reagent for the mild reduction of a variety of bonds. Thus aqueous dimethylformamide solutions of this reagent at room temperature couple benzylic halides, reduce aliphatic monohalides to alkanes, convert vicinal dihalides to olefins, convert geminal halides to carben-oids, reduce acetylenes to /raw5-olefins, and reduce a,j3-unsatu-rated esters, acids, and nitriles to the corresponding saturated derivatives. These conditions also reduce aldehydes to alcohols. The reduction of diethyl fumarate described in this preparation illustrates the mildness of the reaction conditions for the reduction of acetylenes and o ,j8-unsaturated esters, acids, and nitriles. 

Van Wijk and Seeder s viscosity equation, 91 vapour, density of saturated, 324 specific heat of saturated, 336, 346-7, 359 vapour pressure 226 alignment chart, 271 of aliphatic esters, 286 of alkali halides, 237,243 of benzene, 267 boiling-point method for, 235 in capillary tubes, 367 of carbon, 246 centri fugal force, effect of, on 292 constant, 335, 341 over curved surface, 366 determination of, 227-47 dew-point method, 241 of dibasic acids, 243 dynamical method, 235 effusion method, 241. electrification, effect of on, 238, 375 of elements 257 of esters, 250 f., 286 of fusible metal, 230 in... 

Introduction. It will be recalled that one of the most common methods of distinguishing between aromatic and aliphatic hydrocarbons is the difference in the rates of their reactions with sulfuric acid. Aromatic hydrocarbons readily form sulfonic acids when heated with concentrated sulfuric acid at temperatures varying from 80 to 200 . Saturated paraffin hydrocarbons, on the other hand, do not react with sulfuric acid under comparable conditions. A number of saturated paraffins are sulfonated directly by using fuming sulfuric acid and heating under pressure, but the sulfonic acids of the lower paraffin hydrocarbons are prepared by reacting alkyl halides with alkali sulfites. The sulfonic acids of the aromatic hydrocarbons are of much greater importance than the sulfonic acids of paraffins. 

Lithium bromide-Boron trifluoride etherate. Aliphatic ethers can be cleaved by reaction with lithium bromide and boron trifluoride etherate in acetic anhydride at room temperature for 30 hrs. Methoxycyclohexane, for example, is converted into a 7 1 mixture of acetoxycyclohexane and cyclohexene. Saturated steroid ethers are cleaved to mixtures of enes and acetates under these conditions choles-teryl methyl ether gave about equal parts of cholesteryl acetate and cholesteryl bromide. However, Narayanan reports that the lithium halide is not essential and indeed often detrimental. Thus cholesteryl methyl ether treated with boron trifluoride etherate and acetic anhydride in ether at 0° (14 hrs.) gave cholesteryl acetate in 93% yield. 

Alkali hydroxides are most commonly used, with or without a solvent. Suitable solvents, in order of importance, are ethanol, methanol, butanol, ethanol-water mixtures, ethylene glycols and its ethers, glycerol, and hydrocarbons. The usual reagent is saturated ethanolic potassium hydroxide ca. 4n, ca. 20) at room temperature, but always more than the theoretical amount. For dehydrohalogenation of arylalkenyl halides it often suffices to reflux the compound for some time in a suitable solvent, but preparation of purely aliphatic acetylenes sometimes requires heating in an autoclave at temperatures around 170°.180 Reaction times vary, from a few minutes to several hours. 

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