Of allenes

The vibronic coupling model has been applied to a number of molecular systems, and used to evaluate the behavior of wavepackets over coupled surfaces [191]. Recent examples are the radical cation of allene [192,193], and benzene [194] (for further examples see references cited therein). It has also been used to explain the lack of structure in the S2 band of the pyrazine absoiption spectrum [109,173,174,195], and recently to study the photoisomerization of retina] [196],... 

The lithiation of allene can also be carried out with ethyllithium or butyl-lithium in diethyl ether (prepared from the alkyl bromides), using THF as a cosolvent. The salt suspension which is initially present when the solution of alkyllithium is cooled to -50°C or lower has disappeared almost completely when the reaction between allene and alkyllithium is finished. 

The alkylations proceeded much more slowly, when ethyl- or butyllithium in diethyl ether, prepared from the alkyl bromides, had been used for the metallation of allene, in spite of the presence of THF and HMPT as co-solvents. 

Triraethylsilylation of allenyllithium afforded predominantly HCsCCH2SiMe3, while in the cases of the homologues of allene (R = CH3 or primary alkyl) 10-20% contamination by RCsCCHjSiMe3, probably formed by trimethylsilylation of RC(Li )=C=CH2, was present. 

Ojj 1.5068, was obtained in a yield of 82%. The equilibrium mixture obtained in the isomerization under the influence of KO-tert.-61,89 in DHSO consisted of about 70% of allene and 30% of yneamine. Base-catalysed isomerization is therefore not a suitable method to prepare the yneamCne. 

The synthesis of allenes from organocopper compounds and acetylenic acetates was... 

In the first method a secondary acetylenic bromide is warmed in THF with an equivalent amount of copper(I) cyanide. We found that a small amount of anhydrous lithium bromide is necessary to effect solubilization of the copper cyanide. Primary acetylenic bromides, RCECCH Br, under these conditions afford mainly the acetylenic nitriles, RCsCCHjCsN (see Chapter VIII). The aqueous procedure for the allenic nitriles is more attractive, in our opinion, because only a catalytic amount of copper cyanide is required the reaction of the acetylenic bromide with the KClV.CuCN complex is faster than the reaction with KCN. Excellent yields of allenic nitriles can be obtained if the potassium cyanide is added at a moderate rate during the reaction. Excess of KCN has to be avoided, as it causes resinifi-cation of the allenic nitrile. In the case of propargyl bromide 1,1-substitution may also occur, but the propargyl cyanide immediately isomerizes under the influence of the potassium cyanide. 

Synthesis of allenic alcohols hy 1., 2-substitution of chlorine on ether groups by hydride... 

For many years the synthesis and chemical properties of allenes has been a major area of interest in this laboratory. In our NMR research group we studied the H and lie behaviour of these compounds. 

Over the past decade it has been established that for various substituents the i C chemical shift increment is a constitutive property. This applies to many systems e.g. benzenes, alkanes and alkenes. The availability of over 200 allenes, randomly substituted with groups of different nature, enabled us to prove that in the case of allenes the chemical shift increment is a constitutive property too, thus establishing a convenient method for estimating i ( C) values for allenes. 

In Table III a comparison is made between calculated and observed chemical shift values of a variety of allenes that were not included in the data set of Table I,... 

Chemistry of Ketenes, Allenes and Related Compounds", S. Patai (ed.), John Wiley and Sons, Chichester, New York, Brisbane, Toronto, (1980). lOe. H. Hopf, "The Preparation of Allenes and Cumulenes", Chapter 20 in "The Chemistry of Ketenes, Allenes and Related Compounds", S. Patai (ed.), John Wiley and Sons, Chichester, New York, Brisbane, Toronto, (1980). 

Two monomeric and dimeric 2-substituied 7r-allylic complexes (548 and 549) are obtained by treatment of allene with PdCl2(PhCN)2. They are formed by the nucleophilic attack at the central carbon of allene[493, 494],... 

Oxidative cleavage of the complex 549 with CuCri affords 2,3-bis(chloro-methyl)-1,3-butadiene (550) and regenerates PdCri. Thus the preparation of this interesting dimerization product 550 can be carried out with a catalytic amount of PdCl2 and two equivalents of CuCb in MeCN[495], Similarly, treatment of allene with PdBr2 affords the dimeric complex 551. Treatment of this complex with 2 equiv, of bromine yields the dibromide 552. The tetra-bromide 553 is obtained by the reaction of an excess of bromine[496]. Similarly,... 

Carbonylation of the complex 548 proceeds in ethanol gives ethyl 3-chloro-3-butenoate (554), The lactone 555 and the two esters 556 and 557 are obtained by carbonylation of the dimeric complex 549. The oxidative carbonylation of allene in ethanol with PdCl2 gives ethyl itacoante (558), although the yield is low[498]. 

The catalytic oxidative carbonylation of allene with PdCb and CuCh in MeOH affords methyl a-methoxymethacrylate (559)[499]. The intramolecular oxidative aminocarbonylation of the 6-aminoallene 560 affords the unsaturated J-amino ester 561. The reaction has been applied to the enantioselective synthesis of pumiliotoxin (562)[500]. A similar intramolecular oxycarbonyla-tion of 6-hydroxyallenes affords 2-(2-tetrahydrofuranyl)acrylates[501]. 

Allenes also react with aryl and alkenyl halides, or triflates, and the 7r-allyl-palladium intermediates are trapped with carbon nucleophiles. The formation of 283 with malonate is an example[186]. The steroid skeleton 287 has been constructed by two-step reactions of allene with the enol trillate 284, followed by trapping with 2-methyl-l,3-cyclopentanedione (285) to give 286[187]. The inter- and intramolecular reactions of dimethyl 2,3-butenylmalonate (288) with iodobenzene afford the 3-cyclopentenedicarboxylate 289 as a main product) 188]. 

The stoichiometric reaction of allenes with Pd(II) is treated in Chapter 3, Section 9, and catalytic reactions with organic halides are in this chapter, Section 1.1,1.3 Other catalytic reactions of allenes are surveyed in this section. 

Like butadiene, allene undergoes dimerization and addition of nucleophiles to give 1-substituted 3-methyl-2-methylene-3-butenyl compounds. Dimerization-hydration of allene is catalyzed by Pd(0) in the presence of CO2 to give 3-methyl-2-methylene-3-buten-l-ol (1). An addition reaction with. MleOH proceeds without CO2 to give 2-methyl-4-methoxy-3-inethylene-1-butene (2)[1]. Similarly, piperidine reacts with allene to give the dimeric amine 3, and the reaction of malonate affords 4 in good yields. Pd(0) coordinated by maleic anhydride (MA) IS used as a catalyst[2]. 

The cumulated double bonds of an allenic system are of relatively high energy The heat of hydrogenation of allene is more than twice that of propene... 

The three carbons of allene he in a straight line with relatively short carbon-carbon bond distances of 131 pm The central carbon because it bears only two substituents is sp hybridized The terminal carbons of allene are sp hybridized... 

Structural studies show allene to be nonplanar As Figure 10 7 illustrates the plane of one HCH unit is perpendicular to the plane of the other Figure 10 7 also portrays the reason for the molecular geometry of allene The 2p orbital of each of the terminal car bons overlaps with a different 2p orbital of the central carbon Because the 2p orbitals of the central carbon are perpendicular to each other the perpendicular nature of the two HCH units follows naturally... 

The nonplanarity of allenes has an interesting stereochemical consequence 1 3 Disubstituted allenes are chiral they are not superimposable on their mirror images Even an allene as simple as 2 3 pentadiene (CH3CH=C=CHCH3) has been obtained as sep arate enantiomers... 

Assign the allene molecule to a point group and use the character table to form the direct products A-2 x5i,5i X 82,82 xE and E X E. Show how the symmetry species of the point group to which 1,1-dilluoroallene belongs correlate with those of allene. 

Lately a third type of transition state has been favored for [2 + 2] cycloadditions forming carbocyclic and heterocyclic four-membered rings. The experimental data on the addition of diarylketenes to arylethylenes are well accommodated by the [ 2s + 2s + 2s] process proposed by Baldwin (70JA4874). The steric effects on the cycloaddition of allenes to ketenes also favor this mechanism (76JA7698). 

PLC - Programmable logic controller (the registered trade mark of Allen Bradley Co. Inc., USA). 

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