Diallyl Diallylic ether

Table 10. Physical Properties of Some Diallyl Ethers...

This has led to chemical modification of the polyesters, in particular the introduction of allyl ether groups into the resins. Amongst the monomers figuring prominently in the literature are allyl glyceryl ether I, trimethylolpropane diallyl ether II (1,1-diallyloxypropanol) and pentaerythritol triallyl ether III (2,2,2-trial-lyloxyethanol), as shown in Figure 25.32. 

CH2 CH.CH2.OH mw 58.09 OB to C02 -220.35% colorl, mobile liq with a pungent odor mp —129° bp 96.9°, d 0.8520g/cc at 20/4° RI 1.4127, 1.4133, 1.4135 (Sep values). V sol in w, ethanol and ether. Prepn is by the high temp chlorination of propene, followed by hydrolysis of allyl chloride. Thus,. . Allyl chloride is hydrolyzed at 200psi pressure, 150°C and a pH range of 10—12. Injection of steam forms a water-allyl alcohol azeotrope, which is then treated with diallyl ether to remove water. Final purification by distn leads to a 98% min assay. . (Ref 2). Using procedures such as the above, ... at least two American companies (Shell Chemical Co and Dow Chemical Co) produce a total of several million lbs per year... (Ref 2)... 

Diallyl ether had been exposed to air during two weeks before distiliation. The handling was interrupted by a very violent detonation, which was put down to the peroxidation of this ether. 

Ether peroxidation was responsible for the detonation that occurred when dibenzyl ether was treated by the etherate of dichloroaluminium hydride. Note that in this case as well as for diallyl ether there will be easy peroxidation since both sites are of allyl and benzyl nature respectively. 

Dining preparation of diallyl ether by dehydration of the alcohol with sulfuric acid, a violent explosion may occur (possibly involving peroxidation and certainly... 

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). 

Y represents an oxygen atom or a single chemical bond. In the case of diallyl ether double bond isomerization occurs to a considerably higher extent, easily reaching 20 - 30 mole percent [9]. Obviously, reactive terminal C=C double bonds are required to get fast reaction with hydrosiloxane crosslinkers, whereas isomeric inner double bonds exhibit too low a reactivity to be of importance. Another strategy may be helpful. 

Going to extremes, the reactivity of internal acetylenic triple bonds compared with terminal olefinic double bonds was also checked. Diallyl ethers of commercial 2-butyne-l,4-diol and 3-hexyne-2,5-diol are available in high yield by phase transfer etherification. They are reacted under essentially the same conditions as those described in section 3.1, with the double bond now being in 100 percent excess at the beginning (Eq. 4). 

During the study of the isomerization of diallyl ether with catalysts of this type, it was observed that the nature of the complex anion (Y) has a profound influence on the relative rate of isomerization with respect to cyclization. Diallyl ether can be isomerized to a mixture consisting mainly of allyl propenyl ethers (44) with a small amount of 2-methyl-3-methylene-tetrahydrofuran (45) and dipropenyl ether (46) the catalyst for this... 

Asymmetric Cyclizations of 1,6-Heptadiene and of Diallyl Ether Using Catalyst Modified with Epimers of MENTHYL-rerf-BuTYLMETHYLPHospHiNE... 

Real-Time FTIR. For our IR studies, we utilized a stoichiometrically equivalent amount of a trifunctional thiol, trimethylolpropane tris(2-mercaptoacetate), with a difunctional allyl, trimethylolpropane diallyl ether. The thiols were protected from oxidative polymerization by the addition of hydroquinone. The monomers and hydroquinone were purchased from Aldrich Chemicals and were used as received. This formulation was mixed for five minutes and then a commercial photoinitiator, Esacure TZT (Sartomer Inc.), which contained a blend of methyl benzophenones, was added at a level of 1.0% by weight of monomers to the formulation. Stirring was maintained for a further five minutes following the addition of the photoinitiator. The final formulation contained 2.0% by weight of hydroquinone. The samples were prepared prior to each experiment in order to ensure reproducibility of sample history. 

Figure 7. IR spectra of the trimethylolpropane tris(2-mercaptoacetate)/ trimethylolpropane diallyl ether system for three different UV exposure times (0 s, 713 s, 8995 s) showing S-H stretching (2570 cm 1), C=C stretching (1646 cm 1), and aromatic out-of-phase C-H deformation (830 cm 1) peaks. The thiol peak is monitored to calculate the extent of reaction while the C-H deformation peak is used as an internal standard.

The stereoselective isomerization of unsymmetrical diallyl ethers to allyl ( )-vinyl ethers was also carried out in the presence of a cationic iridium(l) catalyst. The catalyst prepared in situ by treating [Ir(cod)(PPh2Me)2]PF6 with hydrogen was found to be an excellent catalyst for the selective isomerization of a less substituted allyl group to an ( )-vinyl ether (Scheme 44).72... 

Failure to achieve the bicyclization of diallyl ether with nBu2ZrCp2 led to the unexpected discovery of the oxidative addition reaction,226 shown in Scheme 44. This reaction has been extensively used for developing synthetically useful reactions, also shown in Scheme 44 232 234>234a-234c Another breakthrough on this topic was made with alkenyl chloride,235 which led to more recent similar discoveries with alkenyl sulfides, sulfones, and ethers236,23611 237 (Scheme 45). 

Allyl 4-toluenesulfonate, 3315 f Allyl vinyl ether, 1904 f 3-Aminopropene, 1254 3-Azidopropene, 1188 f l-Bromo-2-butene, 1548 f 3-Bromo-l-propene, 1153 /V-Chloroallylaminc. 1202 l-Chloro-4-(2-nitrophenyl)-2-butene, 3270 f 3-Chloropropene, 1158 f 3-Cyanopropene, 1465 f Diallylamine, 2450 f Diallyl ether, 2431... 

Many incidents involving explosions have been attributed, not always correctly, to peroxide formation and violent decomposition. Individually indexed incidents are 2-Acetyl-3-methyl-4,5-dihydrothiophen-4-one, 2807 Aluminium dichloride hydride diethyl etherate, Dibenzyl ether, 0061 f 1,3-Butadiene, 1480 f Diallyl ether, 2431 f Diisopropyl ether, 2542... 

Cinnamaldehyde, 3134 f Crotonaldehyde, 1516 f Cyclopropyl methyl ether, 1608 f Diallyl ether, 2431... 

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