Diallyl hexadiene

This unsaturated hydrocarbon is easily prepared by the action of sodium upon allyl iodide or bromide  

Place 56 g. of clean sodium, cut into small pieces, in a 500 ml. round-bottomed flask fitted with two 25 or 30 cm. double surface condensers in series. Weigh out 136 g. (72 ml.) of freshly distilled allyl iodide, b.p. 99-101° (Section 111,39). Introduce about one quarter of the allyl iodide through the condensers. Warm the flask gently until the sodium commences to melt and immediately remove the flame. A vigorous reaction sets in and a liquid refluxes in the condensers. Add 

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Diallyldiozonide (1,5-Hexadienediozonide, Hexadien 1,5-diozonid in Ger). CgHi 0O6, syrupy, explds strongly on heating. Was prepd by Harries Turk by treating a cooled chloro formic soln of diallyl,... 

Alkenes with two reactive carbon-carbon double bonds per molecule like 1,5-hexadiene or diallyl ether are used in the synthesis of silicone compounds which can be later crosslinked by hydrosilylation. A sufficiently high excess of double bonds helps to prevent the dienes from taking part in silane addition across both olefmic ends, but trouble comes from double bond isomerization (Eq. 2). 

Diallyl tellurium, obtained from ally bromide and sodium telluride, decomposed at 180 with formation of biallyl (1,5-hexadiene)2. 

Diolefine, An unsatutated aliphatic hydrocarbon with the general formula Cp,H2 ,3 and two double bonds. Eg diallyl (1,5-hexadiene), CHaiCH.CHs.CHg.CHiCHs Ref Hackh s Diet (1944), p276-L... 

Ein Produktgemisch fallt auoh bei der Photobromierung von Hexadien-(1,5) (Diallyl) an1 5. Naeh IR-spektroskopisehen Messungen besteht die Fraktion der Monobrom-Verbin-dungen zu fiber 65% aus tram- neben 22% cis-l-Brom-hexadien-( 2,5), 3-Brom-hexadien-(1,5) liegt nur zu 11 % vor4. 

Thermal Reaction of Propylene. Thermal reaction of propylene has been studied extensively. Laidler and Wojciechowski (16) reported that main products were ethylene, methane, and hydrogen and that minor ones were ethane, propane, butenes, cyclopentadiene, cyclohexadiene, benzene, toluene, and diallyl at temperatures from 580° to 640°C pressures from 40 to 400 mm Hg in a static system. No allene was detected, which is in contrast to the results obtained at higher temperatures by Szwarc (21) and by Sakakibara (19). Reaction order was determined as 3/2, and the A-factor and activation energy were reported as 1013 34 ml1/2 mole"1/2 sec"1 and 56.7 kcal/mole, respectively. Kallend et ah (9) carried out a detailed analysis of the reaction product at 555° -— 640°C and pressures 7 300 mm Hg. The main C6 compounds present were 1,3-and 1,4-hexadiene. Methylcyclohexene and cyclohexadienes were not found. 

The main reaction modes of (12) are reductive elimination see Reductive Elimination with C C coupling to diallyl (1,5-hexadiene) (equation 42), or nucleophilic displacement... 

Surprisingly allene gave no polymer on reaction with sulfur dioxide [46] but a polymer was prepared from diallyl (1,5-hexadiene) [47]. Some typical diene-sulfiir dioxide copolymers are shown in Table X. 

Allyl radicals were tested as materials or substances that cause cyclization with olefins. 1,5-Hexadiene (diallyl) and diallyl oxalate (DAO) were used as the source materials for allyl radicals. These compounds were subjected to the thermal reaction in the presence of ethylene, which resulted in a rapid formation of five-membered cyclic compounds. The role of allyl radical for the formation of aromatics in pyrolysis reaction is however still... 

Reaction outcomes have been reported for 1,6-hexadiene (W=CH2, X=Br, I), diallyl sulfide (W=S, X=Br, I), diallyl ether (W=0, X=Br, diallyl sulfone (W=S02, X=Br, I), diallylmalonates [W=C(C02R)2, X=C1, Br, ], diallyl sulfonamide (W=N-Ts, X=C1, Br), and diallyl carboxyamide (W=N-C02R, X=C1, Br, ). Changing the steric and electronic character of the olefins can infiuence the regiochemical outcome in these systems. Less-substituted olefins (eq 3), electron-rich acetylenes (eq 4), and allenes (eq 5) react preferentially. Bis-allenic and 1,6-diyne systems also undergo radical cyclization. These factors are exemplified below. 

Terpolymers of ethylene, MA, and diolefins have been obtained by solution polymerization in benzene.The molecular weights of the copolymers increase with increasing proportion of diolefin, and insoluble gel formed at sufficiently high levels of the latter. The typical crosslinking monomers were hexadiene, diallyl ether, and the allyl esters of a,/ -unsatur-ated acids. 

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