Alkynes from dihalides

A simple method for introducing a triple bond into an organic compound is to treat an appropriate dihalide with a strong base. Since vicinal dihalides (usually the bromide) are readily formed by reaction of bromine with an alkene, and geminal dihalides from aldehydes or ketones with phosphorus pentachloride, the method is a useful general procedure for the preparation of terminal and non-terminal alkynes from readily available starting materials. 

Vicinal dihalides from alkenes and alkynes (Geigert et al. 1983b) ... 

It was found that the system tcrt-BuOH/0.1 mol% 18C6/petroleum ether is also very useful in alkyne synthesis, starting from 1,2-dihalides (from alkenes) or 1,1-dihalides (from aldehydes or ketones). Advantages are high yields and fairly mild reaction conditions [232,233]. 

Alkynes can be prepared by the elimination of HX from alkyl halides in much the same manner as alkenes (Section 7.1). Treatment of a 1,2-dihaloaJkane (a vicinal dihalide) with excess strong base such as KOH or NaNH2 results in a twofold elimination of HX and formation of an alkyne. As with the elimination of HX to form an alkene, we ll defer a discussion of the mechanism until Chapter 11. 

The necessary vicinal dihalides are themselves readily available by addition of Br2 or Cl2 to alkenes. Thus, the overall halogenation/dehvdrohalogenation sequence makes it possible to go from an alkene to an alkyne. for example, diphenylethylene is converted into diphenylacetylene by reaction with Br2 and subsequent base treatment. 

An alkyne is a hydrocarbon that contains a carbon-carbon triple bond. Alkyne carbon atoms are sp-hybridized, and the triple bond consists of one sp-sp a bond and two p-p tt bonds. There are relatively few general methods of alkyne synthesis. Two good ones are the alkylation of an acetylide anion with a primary-alkyl halide and the twofold elimination of HX from a vicinal dihalide. 

The chemistry of alkynes is dominated by electrophilic addition reactions, similar to those of alkenes. Alkynes react with HBr and HC1 to yield vinylic halides and with Br2 and Cl2 to yield 1,2-dihalides (vicinal dihalides). Alkynes can be hydrated by reaction with aqueous sulfuric acid in the presence of mercury(ll) catalyst. The reaction leads to an intermediate enol that immediately isomerizes to yield a ketone tautomer. Since the addition reaction occurs with Markovnikov regiochemistry, a methyl ketone is produced from a terminal alkyne. Alternatively, hydroboration/oxidation of a terminal alkyne yields an aldehyde. 

Digitoxigenin, structure of, 1097 Digitoxin, structure of, 989 Dihalide, alkynes from, 261 Dihedral angle, 94 Diiodomelhane. Simmons-Smith reaction with, 228-229 Diisobutylaluminum hydride, reaction with esters, 812 structure of, 699 Diisopropylamine, pK.d of, 923 1,3-Diketone, pfCa of, 852 Dimethyl disulfide, bond angles in, 20 structure of, 20 Dimethyl ether, electrostatic... 

Alkynes are prepared from alkyl dihalides via elimination of atoms or groups from adjacent carbons. Dehydrohalogenation of vicinal- or gemiwaZ-dihahdes is a particularly useful method for the preparation of alkynes (see Section 5.4.5). 

When terminal alkynes are used as substrates, alkylcoppermagnesium dihalides prepared from a cop-peril) bromide-dimethyl sulfide complex typically are used (e.g. equation 31134 and Scheme 7).135 The choice of a Grignard reagent, from which the alkylcopper(I) species is prepared, is important in this instance, alkyllithium-derived alkylcopper reagents usually are less satisfactory.10... 

In some cases, we can generate a carbon-carbon triple bond by eliminating two molecules of HX from a dihalide. Dehydrohalogenation of a geminal or vicinal dihalide gives a vinyl halide. Under strongly basic conditions, a second dehydrohalogenation may occur to form an alkyne. 

If 2 moles of halogen add to 1 mole of an alkyne, a tetrahalide results. Sometimes it is difficult to keep the reaction from proceeding all the way to the tetrahalide even when we want it to stop at the dihalide. 

Thus, for example, the direct conversion of an ether into an acetal or ketal is difficult to achieve whereas the oxidation of an alcohol to an aldehyde or ketone (or the reverse process) is a trivial transformation. Similarly, the transition from an oxidation level of 2 to level 1 is problematic in the case when one tries to convert dihalides into monohalides while the transformation of alkynes into alkenes may be safely considered a viable route to carry out this transition. 

Alkynes are prepared by elimination reactions, as discussed in Section 8.10. A strong base removes two equivalents of HX from a vicinal or geminal dihalide to yield an alkyne by two... 

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