Of allylic alcohols

An example of this t3T)e of reaction which does not produce a byproduct is the production of allyl alcohol from propylene oxide ... 

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°. 

Allyl Iodide. Use 29 g. (34 ml.) of allyl alcohol and 340 g. (200 ml.) of 57 per cent, hydriodic acid 84 g. of crude iodide are obtained. Upon adding 29 g. (34 ml.) of allyl alcohol to the combined residue in the flask and the aqueous layer and distilling as before, a further 72 g. of crude allyl iodide may be isolated. B.p. 99-101° (mainly 100°). The compound is very sensitive to light the distillation should therefore be conducted in a darkened room and preferably in the presence of a little silver powder. 

Diasterocontrolled hydrogenation of allylic alcohols directed by the -OH group... 

Hydrogenation of olefins, enols, or enamines with chiral tVilkinson type catalysts, e.g., Noyort hydrogenation. Hydroboration of olefins with chiral boranes. Sharpless epoxi-dation of allylic alcohols. 

When allylic alcohols are used as an alkene component in the reaction with aryl halides, elimination of /3-hydrogen takes place from the oxygen-bearing carbon, and aldehydes or ketones are obtained, rather than y-arylated allylic alcohoIs[87,88]. The reaction of allyl alcohol with bromobenzene affords dihydrocinnamaldehyde. The reaction of methallyl alcohol (96) with aryl halides is a good synthetic method for dihydro-2-methylcinnamaldehyde (97). 

Some nucleophiles other than carbon nucleophiles are allylated. Amines are good nucleophiles. Diethylamine is allylated with allyl alcohol[7]. Allylammes are formed by the reaction of allyl alcohol with ammonia by using dppb as a ligand. Di- and triallylamines are produced commercially from allyl alcohol and ammonia[l74]. 

Carbonylation of allylic alcohols requires severe conditions[248]. The carbonylation of allylic alcohols proceeds smoothly in the presence of LiCl and Ti(IV) isopropoxide[249j. The allylic methyl ether 394 can be carbonylated with the use of PdCl2[250] or 7r-allylpalladium coordinated by BF4, PF, and... 

The cyclohexadiene derivative 130 was obtained by the co-cyclization of DMAD with strained alkenes such as norbornene catalyzed by 75[63], However, the linear 2 1 adduct 131 of an alkene and DMAD was obtained selectively using bis(maleic anhydride)(norbornene)palladium (124)[64] as a cat-alyst[65], A similar reaction of allyl alcohol with DMAD is catalyzed by the catalyst 123 to give the linear adducts 132 and 133[66], Reaction of a vinyl ether with DMAD gives the cyclopentene derivatives 134 and 135 as 2 I adducts, and a cyclooctadiene derivative, although the selectivity is not high[67]. 

By-product acetic acid is obtained chiefly from partial hydrolysis of cellulose acetate [9004-35-7]. Lesser amounts are obtained through the reaction of acetic anhydride and cellulose. Acetylation of saHcyHc acid [69-72-7] produces one mole of acetic acid per mole of product and the oxidation of allyl alcohol using peracetic acid to yield glycerol furnishes by-product acid, but the net yield is low. 

Ma.nufa.cture. Most butanediol is manufactured in Reppe plants via hydrogenation of butynediol. Recendy an alternative route involving acetoxyiation of butadiene has come on stream and, more recendy, a route based upon hydroformylation of allyl alcohol. Woddwide butanediol capacity has climbed steadily for many years. In 1990 it was estimated to be 428,000 metric tons (141), as compared to a Htde more than 70,000 metric tons in 1975... 

Propylene oxide-based glycerol can be produced by rearrangement of propylene oxide [75-56-9] (qv) to allyl alcohol over triUthium phosphate catalyst at 200—250°C (yield 80—85%) (4), followed by any of the appropriate steps shown in Figure 1. The specific route commercially employed is peracetic acid epoxidation of allyl alcohol to glycidol followed by hydrolysis to glycerol (5). The newest international synthesis plants employ this basic scheme. 

More recendy, however, the technology of introducing a new functional group to the double bond of allyl alcohol has been developed. Adyl alcohol is accordingly used as an intermediate compound for synthesizing raw materials such as epichlorohydrin and 1,4-butanediol, and this development is bringing about expansion of the range of uses of allyl alcohol. 

Table 1. A2eotropic Boiling Points of Allyl Alcohol—Water—Organic Solvent Systems...

From Allyl Alcohol. The reaction of allyl alcohol [107-18-6] with chlorine and water gives a mixture of glycerol m on ochl orohydrin s consisting of 73% 3-chloropropane-l,2-diol and 27% of 2-chloropropane-l,3-diol (57). In a recycle reaction system in which allyl alcohol is fed as a 4.5—5.5 wt % solution, chlorine is added at a rate of 7—9 moles per hour. The reaction time is about five seconds, the reaction temperature 50—60°C and the recycle ratio is 10—20 1. Under these conditions m on ochl orohydrin s have been obtained in 88% yield with 9% dichlorohydrins (58) (see Allyl ALCOHOL AND DERIVATIVES). 

From Allyl Alcohol. An alternative route to dichlorohydrias from aHyl chloride begias with the hydrolysis to aHyl alcohol. Significant yields of 2,3-dichloropropanol can be obtained from the reaction of chlorine with allyl alcohol if the reaction is performed ia the presence of concentrated hydrochloric acid (65). Several patents for the manufacture of 2,3-dichloropropanol by the chlorination of allyl alcohol at low temperature, —30° to +20° C, ia 25—40% HCl solution have appeared (66—68). Product yields as high as 98% are claimed. 

Oxiranes react with iodotrimethylsilane to give silylated halo alcohols e.g. 60) which can be converted to allylic alcohols (Scheme 53) (80JOC2579, 80TL2329) cf. other syntheses of allylic alcohols (Sections 5.05.3.2.2, 5.05.3.4.3(0 and Hi)). 

The remarkable stereospecificity of TBHP-transition metal epoxidations of allylic alcohols has been exploited by Sharpless group for the synthesis of chiral oxiranes from prochiral allylic alcohols (Scheme 76) (81JA464) and for diastereoselective oxirane synthesis from chiral allylic alcohols (Scheme 77) (81JA6237). It has been suggested that this latter reaction may enable the preparation of chiral compounds of complete enantiomeric purity cf. Scheme 78) ... 

This example shows that overoxidation of allylic alcohols may occur with DDQ. ... 

A number of useful resins have been prepared from allyl compounds, i.e. derivatives of allyl alcohol CH2 = CH CH20H. One of these, diethylene glycol... 

In comparison with manganese dioxide, the DDQ reagent has several advantages for the oxidation of allylic alcohols. The quinone method is more reproducible only one equivalent of oxidant need be added and generally fewer side reactions are observed. On the other hand, the workup of DDQ reactions often requires chromatography and in the simpler cases lower isolated yields may be realized. 

Nickel peroxide is a solid, insoluble oxidant prepared by reaction of nickel (II) salts with hypochlorite or ozone in aqueous alkaline solution. This reagent when used in nonpolar medium is similar to, but more reactive than, activated manganese dioxide in selectively oxidizing allylic or acetylenic alcohols. It also reacts rapidly with amines, phenols, hydrazones and sulfides so that selective oxidation of allylic alcohols in the presence of these functionalities may not be possible. In basic media the oxidizing power of nickel peroxide is increased and saturated primary alcohols can be oxidized directly to carboxylic acids. In the presence of ammonia at —20°, primary allylic alcohols give amides while at elevated temperatures nitriles are formed. At elevated temperatures efficient cleavage of a-glycols, a-ketols... 

Oppenauer oxidation, 236 Oxidation of allylic alcohols with dichloro-dicyanobenzoquinone, 248 Oxidation of allylic alcohols with manganese dioxide, 247... 

Mixtures of anhydrous hydrogen fluoride and tetrahydrofuran are successfully used as fluorinating agents to convert 1,1,2-trifluoro-l-allcen-3-ols, easily prepared from bromotrifluoroethene via lithiation followed by the reaction with aldehydes or ketones, to 1,1,1,2-tetrafluoro-2-alkenes The yields are optimal with a 5 1 ratio of hydrogen fluoride to tetrahydrofuran The fluorination reaction involves a fluonde lon-induced rearrangement (Sf,j2 mechanism) of allylic alcohols [65] (equation 40)... 

Allyiic rearrangements are observed m the reactions of allylic alcohols with dialkylaminosulfur trifluorides [95 130] Both crotyl alcohol and buten 3 ol give... 

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