The Prins Reaction

Another addition to polymers with main-chain unsaturation is the Prins reaction between ethylenic hydrocarbons and compounds containing aldehydic carbonyl groups. Kirchof in 1923, described the reaction of natural rubber in benzene solution with aqueous formaldehyde in the presence of concentrated sulfuric acid. The general reaction of an aldehyde, RCHO, with a polyisoprene in the presence of an inorganic or organic acid or an anhydrous metal salt, is represented by 

In the absence of such catalysts, the reaction leads to a shift in the double 

These reactions can be carried out in solution or in dispersion or by reaction in the solid phase (Cunneen and Porter, 1965) in the last case it is again dilHcult to differentiate the Prins reaction from mechanochemical reactions initiated by chain rupture during mastication. 

Other aldehydic compounds, such as glyoxal and chloral, also react in a similar way with polyisoprenes and unsaturated rubbers (e.g., poly(cfs-l,4-isoprenes), poly( fs-l,4-butadiene), and copolymers of isobutylene and iso-prene). The use of strong acids, or Lewis acids, causes complications, as the acids themselves, under suitable conditions, catalyze cyclization and cis-trans isomerization, and these reactions may occur simultaneously with the addition reactions. 

The microenvironmental effect of various sulfonated polystyrene beads was studied using the Prins reaction as a probe.372 Reaction rates were found to be lower when carbomethoxy or carbobutoxy neighboring groups were present compared to phenyl. A less ionic microenvironment appears to allow for a higher concentration of styrene within the polymer and leads to an immediate reaction with protonated formaldehyde. 

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A commercial process based on the Prins reaction is the synthesis of isoprene from isobutylene and formaldehyde through the intermediacy of 4,4-dimethyl-l,3-dioxane (49—51) ... 

Uses ndReactions. The Prins reaction of 3-carene with formaldehyde in acetic acid gives mainly 2-carene-4-methanol acetate, which when saponified produces the 2-carene-4-methanol, both of which are commercial products of modest usage (60). 3-Carene (28) also reacts with acetic anhydride with a catalyst (ZnCl2) to give 4-acetyl-2-carene (29) (61), which is also a commercial product. Although 3-carene does not polymerize to produce terpene resins, copolymerization with phenol has been successfully commercialized by DRT in France (62). 

The Prins reaction with formaldehyde, acetic acid, acetic anhydride, and camphene gives the useful alcohol, 8-acetoxymethyl camphene, which has a patchouli-like odor (83). Oxidation of the alcohol to the corresponding aldehyde also gives a useful iatermediate compound, which is used to synthesize the sandalwood compound dihydo- P-santalol. 

Longifolene. There are at least four commercially important aroma chemicals made from (+)-1ongifo1ene and about thirteen products made from (-)-isolongifolene (90) (182). Acetoxymethyl longifolene or the formate are formed during the Prins reaction on (+)-1ongifo1ene. Saponification of the esters gives the useful perfumery alcohol (183) (Fig. 9). 

The Prins reaction on isolongifolene has also produced a number of useful products (185,186). All the products have amber, woody odors, and are known under the names of Amborol, Amboryl Formate, and Amboryl Acetate. 

Formaldehyde also reacts with butadiene via the Prins reaction to produce pentenediols or their derivatives. This reaction is cataly2ed by a copper-containing catalyst in a carboxyUc acid solution (57) or RuCl (58). The addition of hydrogen also proceeds via 1,2- and 1,4-addition. 

The Prins reaction often yields stereospecifically the and-addition product this observation is not rationalized by the above mechanism. Investigations of the sulfuric acid-catalyzed reaction of cyclohexene 8 with formaldehyde in acetic acid as solvent suggest that the carbenium ion species 7 is stabilized by a neighboring-group effect as shown in 9. The further reaction then proceeds from the face opposite to the coordinating OH-group " ... 

This type of polyhalo alkane adds to halogenated alkenes in the presence of AICI3 by an electrophilic mechanism. This is called the Prins reaction (not to be confused with the other Prins reaction, 16-53). ... 

The addition of an alkene to formaldehyde in the presence of an acid catalyst is called the Prins reaction.Three main products are possible which one predominates depends on the alkene and the conditions. When the product is the 1,3-diol or the dioxane, the reaction involves addition to the C=C as well as to the C=0. The mechanism is one of electrophilic attack on both double bonds. The acid first protonates the C=0, and the resulting carbocation attacks the C=C ... 

The Prins reaction has also been carried out with basic catalysts Griengl, H. Sieber, W. Monatsh. Chem., 1973, 104, 1008, 1027. 

Ene and Carbonyl-Ene Reactions. Certain double bonds undergo electrophilic addition reactions with alkenes in which an allylic hydrogen is transferred to the reactant. This process is called the ene reaction and the electrophile is known as an enophile A When a carbonyl group serves as the enophile, the reaction is called a carbonyl-ene reaction and leads to [3,-y-unsalurated alcohols. The reaction is also called the Prins reaction. 

Cationic polymerization of alkenes and alkene derivatives has been carried out frequently in aqueous media.107 On the other hand, the reaction of simple olefins with aldehydes in the presence of an acid catalyst is referred to as the Prins reaction.108 The reaction can be carried out by using an aqueous solution of the aldehyde, often resulting in a mixture of carbon-carbon bond formation products.109 Recently, Li and co-workers reported a direct formation of tetrahydropyranol derivatives in water using a cerium-salt catalyzed cyclization in aqueous ionic liquids (Eq. 3.24).110... 

Reactions of the allylic position of alkenes with carbonyl or imine electrophiles are known as Prins reactions and have been discussed in previous sections (3.2.9). More examples of similar Alder-ene-type reactions (the Prins reaction) will be discussed in Chapter 8. 

Protonic acid and Lewis acids can activate carbonyls to facilitate the addition of nucleophile attacks in aqueous media. The Prins reaction, reaction with alkyne, and Friedel-Crafts-type reactions have been discussed in related chapters in detail. 

Other nucleophilic additions conducted in aqueous media can be found in the literature (Lubineau et al., 1994 Strauss, 1999). These reactions will include the benzoin condensation, the Prins reaction, and the Wittig-Horner reaction, and the Baeyer-Villi-ger oxidation. 

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