Allyl chloride hydrogenation

Propene Chlorine Allyl chloride Hydrogen chloride... 

Allylsilanes are known as interesting and useful reagents for organic synthesis.85-88 Hurd first reported the direct reaction of elemental silicon with allyl chloride in the presence of copper catalyst to give a mixture of allylchlorosilanes and polymeric materials.15 Among the volatile compounds, allyltrichlorosilane, formed by the 1 1 1 reaction of allyl chloride, hydrogen chloride and elemental silicon, was observed as the major product instead of the normally expected diallyldichlorosilane. Since diallyldichlorosilane thermally polymerizes at temperatures above 130°C, the product mixture polymerized during the reaction or upon distillation. 

When elemental silicon was reacted with a mixture of allyl chloride and hydrogen chloride in the presence of copper catalyst using a stirred reactor equipped with a spiral band agitator (Fig. 1) at temperatures ranging from 220 to 320 °C, allyldichlorosilane was successfully obtained as the major product along with allyltrichlorosilane as a minor product. Allyldichlorosilane was produced by the 1 1 1 reaction of allyl chloride, hydrogen chloride, and elemental silicon (Eq. 12).27... 

Allyl Chloride. Comparatively poor yields are obtained by the zinc chloride - hydrochloric acid method, but the following procedure, which employs cuprous chloride as a catalyst, gives a yield of over 90 per cent. Place 100 ml. of allyl alcohol (Section 111,140), 150 ml. of concentrated hydrochloric acid and 2 g. of freshly prepared cuprous chloride (Section II,50,i one tenth scale) in a 750 ml. round-bottomed flask equipped with a reflux condenser. Cool the flask in ice and add 50 ml. of concen trated sulphuric acid dropwise through the condenser with frequent shaking of the flask. A little hydrogen chloride may be evolved towards the end of the reaction. Allow the turbid liquid to stand for 30 minutes in order to complete the separation of the allyl chloride. Remove the upper layer, wash it with twice its volume of water, and dry over anhydrous calcium chloride. Distil the allyl chloride passes over at 46-47°. 

Reaction Mechanism. High temperature vapor-phase chlorination of propylene [115-07-17 is a free-radical mechanism in which substitution of an allyhc hydrogen is favored over addition of chlorine to the double bond. Abstraction of allyhc hydrogen is especially favored since the allyl radical intermediate is stabilized by resonance between two symmetrical stmctures, both of which lead to allyl chloride. 

The production of allyl chloride could be effected by direct chlorination of propylene at high temperatures (approximately 500°C and one atmosphere). The reaction substitutes an allylic hydrogen with a chlorine atom. Hydrogen chloride is a by-product from this reaction ... 

After succeeding in the direct synthesis of allyidichlorosilane hy reacting elemental silicon with a mixture of allyl chloride and hydrogen chloride in 1993," Jung el cil. reinvestigated the Friedel-Crafts reactions of benzene derivatives with allyidichlorosilanes in detail (Eq. (2)). 

Photolytic. Distilled water irradiated with UV light (X = 290 nm) yielded the following photolysis products 2-chloro-l-propanol, allyl chloride, allyl alcohol, and acetone. The photolysis half-life in distilled water is 50 min, but in distilled water containing hydrogen peroxide, the half-life decreased to <30 min (Milano et al, 1988). 

In the absence of potassium hydroxide hydrogenation of vinylic and allylic chlorides to the saturated chlorides (with only partial or no hydrogenolysis of chlorine) is accomplished over 5% platinum, 5% palladium and, best of all, 5% rhodium on alumina [40]. 

Alkyl halides possessing / -hydrogens are usually poor substrates for carbonylative cross-coupling due to competitive / -hydride elimination/ Allyl chlorides can be used in carbonylative cross-coupling with allylstannanes/ phenyl-, 3-furyl, or vinylstannanes " to afford allylketones in modest to good yields. Divinylketones can be accessed through the reaction of vinylstannanes with vinyl iodides or vinyl triflates, with the latter requiring the addition of LiCl. Synthetic potential of this method has been proved in the formation of macrocyclic ketone jatrophone. In the reaction of vinyl triflates with tetramethyltin or aryltrimethylstannanes the additional activation by ZnCle is required. 

These can be prepared by a) asymmetric dihydroxylation of allylic chlorides followed by acetonide formation and elimination with BuLi b) catalytic asymmetric transfer hydrogenation and c) reduction of alkynones with chiral metal hydrides, (a) Marshall, J. A. Jiang, H. Tetrahedron Lett. 1998, 39, 1493 Yadav, J. S. Chander, M. C. Rao, C. S. Tetrahedron Lett. 1989, 30, 5455 (b) Matsumura, K. Hashiguchi,... 

There are four processes for industrial production of allyl alcohol. One is alkaline hydrolysis of allyl chloride. A second process has two steps. The first step is oxidation of propylene to acrolein and the second step is reduction of acrolein to allyl alcohol by a hydrogen transfer reaction, using isopropyl alcohol. At present, neither of these two processes is being used industrially. Another process is isomerization of propylene oxide. Until 1984. all allyl alcohol manufacturers were using this process. Since 1985 Showa Denko K.K. has produced allyl alcohol industrially by a new process which they developed- This process, which was developed partly for the purpose of producing epichlorohydrin via allyl alcohol as the intermediate, has the potential to be the main process for production of allyl alcohol. The reaction scheme is as follows ... 

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