Elimination of 3-Hydrogen

Another reaction in the last step is the syn elimination ofhydrogen with Pd as H—Pd—X, which takes place with alkyl Pd complexes, and the Pd hydride and an alkene are formed. The insertion of an alkene into Pd hydride and the elimination of, (3-hydrogen are reversible steps. The elimination of, 3-hydrogen generates the alkene, and both the hydrogen and the alkene coordinate to Pd, increasing the coordination number of Pd by one. Therefore, the / -elimination requires coordinative unsaturation on Pd complexes. The, 3-hydrogen eliminated should be syn to Pd. 

The elimination of 3-hydrogen of Pd alkoxide (17) to afford a carbonyl compound is a similar reaction. 

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Present in citronella and valerian oils, tur penline, ginger, rosemary and spike oils. It is produced artificially by the elimination of hydrogen chloride from bornyl chloride (artifi cial camphor) or from isobornyl chloride, by the dehydrogenation of borneol and isobor-neol and by the action of elhanoic anhydride on bornylamine. Chiral. 

Purification of refinery gases by elimination of hydrogen sulfide as well as Claus units for sulfur recovery began to make their appearance. 

The presence of the base brings about the irreversible elimination of hydrogen chloride between the acid chloride and the acid the resulting p3rridine hydrochloride precipitates out as the reaction progresses. 

The majority of preparative methods which have been used for obtaining cyclopropane derivatives involve carbene addition to an olefmic bond, if acetylenes are used in the reaction, cyclopropenes are obtained. Heteroatom-substituted or vinyl cydopropanes come from alkenyl bromides or enol acetates (A. de Meijere, 1979 E. J. Corey, 1975 B E. Wenkert, 1970 A). The carbenes needed for cyclopropane syntheses can be obtained in situ by a-elimination of hydrogen halides with strong bases (R. Kdstcr, 1971 E.J. Corey, 1975 B), by copper catalyzed decomposition of diazo compounds (E. Wenkert, 1970 A S.D. Burke, 1979 N.J. Turro, 1966), or by reductive elimination of iodine from gem-diiodides (J. Nishimura, 1969 D. Wen-disch, 1971 J.M. Denis, 1972 H.E. Simmons, 1973 C. Girard, 1974),... 

Phosphoms halides are subject to reactions with active hydrogen compounds and result in the elimination of hydrogen halide. They are convenient reagents in the synthesis of many esters, amides, and related compounds. However, because the involved hydrogen halide frequendy catalyzes side reactions, it is usually necessary to employ a hydrogen halide scavenger to remove the by-product. 

The manufacture and uses of oxiranes are reviewed in (B-80MI50500, B-80MI50501). The industrially most important oxiranes are oxirane itself (ethylene oxide), which is made by catalyzed air-oxidation of ethylene (cf. Section 5.05.4.2.2(f)), and methyloxirane (propylene oxide), which is made by /3-elimination of hydrogen chloride from propene-derived 1-chloro-2-propanol (cf. Section 5.05.4.2.1) and by epoxidation of propene with 1-phenylethyl hydroperoxide cf. Section 5.05.4.2.2(f)) (79MI50501). 

Diaziridinones (167) are obtained from di-t-alkylureas by Af-chlorination and base-promoted elimination of hydrogen chloride from (279) (69JOC2254). The very unstable c/s-fused diaziridinone (280) could be prepared by a similar but milder procedure (76JOC2813). 

Dehydrochlorination begins at about 120°C. The temperature is raised about lO C/hr to 150 C to avoid vigorous gas evolution. The elimination of hydrogen chloride is complete after 5-6 hr. 

There are several methods for generation of benzyne in addition to base-catalyzed elimination of hydrogen halide from a halobenzene, and some of these are more generally applicable for preparative work. Probably the most convenient method is diazotization of o-aminobenzoic acid. Concerted loss of nitrogen and carbon dioxide follows diazotization and generates benzyne. Benzyne can be formed in this manner in the presence of a variety of compounds with which it reacts rapidly. 

Joly s method (or modifications) is the best procedure for preparing A " -3-ketones and can be extended to the elimination of hydrogen bromide from a-bromo ketones of all types. Rearrangement is sometimes observed but is not often serious. Selectivity can be improved in some instances by lowering the reaction temperature. The method has been found useful for the preparation of A" -3-ketones from 6-halo-A" -3-ketones ... 

Although an old method, the elimination of hydrogen halide from isolated halides is still occasionally recommended. An example is the formation of cholest-2-ene (108) from 3j5-chloro-5a-cholestane, followed by purification via the dibromide (ref. 185, p. 252). 

The primary product of hypohalite photolysis is a 1,5-halohydrin, the stability of which increases on passing from iodo- to bromo- to chloro-hydrins. If spontaneous elimination of hydrogen halide does not occur, the halohydrins can be converted into tetrahydrofurans by base treatment. In several instances it has been possible to isolate the intermediate... 

Note 1. An alternative procedure proceeds by oxidation of the 3/5-hydroxy group with chromic acid-sulfuric acid and subsequent elimination of hydrogen chloride by treatment of the intermediate chloroketone with potassium acetate in methanol. Good overall yields are obtained with this reaction sequence in the androstane series. 

Trifluoromethyl groups are very resistant to hydrolysis, unless they are allylic or benzylic, or vicinal to a carbon linked to hydrogen. In the last case, elimination of hydrogen fluonde leads to the formation of a difluoromethylene group which is key to additional reactions... 

Elimination of hydrogen chloride from 1,1-dichloromethyl sulfide with potassium tcrt-butoxide affords chloromethylthiocarbene [J] (equation 5)... 

Dehydrochlorination of bis(tnfluoromethylthio)acetyl chloride with calcium oxide gives bis(trifluoromethylthio)ketene [5] (equation 6) Elimination of hydrogen chloride or hydrogen bromide by means of tetrabutylammonium or potassium fluoride from vinylic chlorides or bromides leads to acetylenes or allenes [6 (equation 7) Addition of dicyclohexyl-18-crown-6 ether raises the yields of potassium fluoride-promoted elimination of hydrogen bromide from (Z)-P-bromo-p-ni-trostyrene in acetonitrile from 0 to 53-71 % In dimethyl formamide, yields increase from 28-35% to 58-68%... 

Elimination of hydrogen chloride from 2/f perfluoro-2-methylpropane-1 -sulfenyl chloride by the triethylamine-boron trifluoride complex results in cyclization to perfluoro-l,l-dimethylthiirane (perfluoroisobutylene sulfide) [, 9] (equation 9)... 

As expected, elimination of hydrogen fluoride in most cases is considerably more difficult In bimolecular reactions, the rates are about 2-3 orders of magnitude lower than those of hydrogen chlonde and about 4-5 orders of magnitude lower than those of hydrogen bromide [10]... 

With highly fluorinated compounds, even relatively weak bases cause elimination of hydrogen fluoride Such reagents are especially desnable in dehydro-fluonnations of polyfluoro compounds containing functionalities that would suffer from stronger bases [21 (equation 19)... 

Elimination of hydrogen fluoride from vinylic fluorides yields allenes [2J] or acetylenes [24] (equations 21 and 22)... 

The last example represents a fairly rare elimination of hydrogen fluoride in preference to hydrogen chloride, a reaction that deserves a more detailed discussion A comparison of bond dissociation energies of carbon-halogen bonds shows that the carbon-fluorine bond is much stronger than the carbon-chlorine, carbon-bromine, and carbon-iodme bonds 108-116, 83 5, 70, and 56 kcal/mol, respec-... 

The ratios of the rates of elimination of hydrogen halides depend evidently on the structure of the halogenated compound and span many orders of magnitude The rate of dehydrofluonnation w much slower than that of dehydrochlonnation, dehydrobromination and dehydrolodination However, there are exceptions... 

It IS interesting that the rates of elimination of hydrogen fluoride from all fluormated succinic acids span hardly 1 order of magnitude, whereas the rates of preferential dehydrofluorination of both a-bromo-a -fluorosuccimc acids are higher by almost 2 orders of magnitude [35, 36, 37, 38] (Table 3)... 

From the thorough studies of the mechanism of elimination of hydrogen halides from vicinal fluorohalo compounds, it follows that the result of elimination depends on the stabihty of the carbanionic species in which the negative charge is on the carbon P to fluorine and a to chlorine or bromine [43, 44, 45, 46, 47, 48, 49, 50, 51. 52, 53, 54]... 

Preferential elimination of hydrogen fluonde from vicinal halofluoro compounds occurs also in the cyclohexane series [55 56, 57], acenaphthene series [55], and benzodihydrofuran series [59 60] Here, the strength of the base and the stereochemistry play important roles... 

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