Resorcinol chemistry

Ciullo PA, Hewitt N (1999) The rubber formulary. Noyes, Norwich Coker K (2001) Modeling of chemical kinetics and reactor design. Gulf, Boston, MA Davis FJ (2004) Polymer chemistry a practical approach. Oxford University Press, Oxford Drobny JG (2001) Technology of fluoropolymers. CRC Press, Boca Raton, FL Durairaj RB (2005) Resorcinol chemistry technology and applications. Springer, Berlin Dutcher JR et al (eds) (2005) Soft materials structure and dynamics. Marcel Dekker, New York Erbil HY (2000) Vinyl acetate emulsion polymerization and copolymeiization with acrylic monomers. CRC Press, Boca Raton, FL... 

Durairaj R (2005) Resorcinol Chemistry, Technology and Applications. Springer, Germany 186-187. 

Resorcinol chemistry can aid in developing high barrier polymeric materials, according to Indspec Chemical Corp. Three relevant derivatives are resorcinol dioxyacetic acid (RDOA), bis-(hydroxyethyl)-ether of resorcinol (HER) and resorcinol diglycidyl ether (RDGE). 

A reexamination of polycarbonate chemistry was carried out about 50 years after the first aromatic polycarbonates of resorcinol and hydroquinone were discovered. In independent investigations at Bayer AG and General Electric, it was discovered that the polycarbonates of BPA could be prepared (eq. 2). Unlike the ahphatic polycarbonates prepared earlier, which were either hquids or low melting sohds, the aromatic polycarbonates were amorphous sohds having elevated glass-transition temperatures. 

The close electrochemical relationship of the simple quinones, (2) and (3), with hydroquinone (1,4-benzenediol) (4) and catechol (1,2-benzenediol) (5), respectively, has proven useful in ways extending beyond their offering an attractive synthetic route. Photographic developers and dye syntheses often involve (4) or its derivatives (10). Biochemists have found much interest in the interaction of mercaptans and amino acids with various compounds related to (3). The reversible redox couple formed in many such examples and the frequendy observed quinonoid chemistry make it difficult to avoid a discussion of the aromatic reduction products of quinones (see Hydroquinone, resorcinol, and catechol). 

As polymer chemistry advanced in the 1930s and 1940s, stronger and more durable synthetic adhesives such as early phenol, resorcinol and urea formaldehydes began to supplant natural glues in wood aircraft manufacture. Around this time however, metal began to replace wood as the dominant material for aircraft manufacture. Aerospace adhesives research and development moved on to focus on metals, primarily aluminum, as the substrates of interest. 

Catechol is also obtained from coal coking and from certain wood residues. Vanillin (synthetic vanilla flavoring) is a catechol derivative. Resorcinol and hydroquinone are currently made by the same type of chemistry used... 

Our task was to develop a feasible synthesis for diamino resorcinol. From several possibilities [1-4] the resorcinol and anihne were chosen as starting materials. The diazotated aniline was coupled with resorcinol among basic conditions giving 4,6-bisphenylazo resorcinol. Hydrogenation of the latter resulted in diamino resorcinol and aniline, which could be recycled (scheme 14.2). This chemistry is well known [5-13] therefore, the research work focused on finding the optimal parameters and catalyst and finally on elaborating a process for scale-up. 

Hessel V, Hofmann C, Lob P, Lohndorf J, Lowe H, Ziogas A (2005b) Aqueous Kolbe-Schmitt synthesis using resorcinol in a micro-reactor laboratory rig under high-p,T conditions. Org Proc Res Dev 9 479 189 Hessel V, Lob P, Lowe H (2005c) Development of microstructured reactors to enable organic synthesis rather than subduing chemistry. Curr Org Chem 9 765-787... 

The chemistry shown in Scheme 13 has been applied to the synthesis of 5-substituted resorcinols, interesting naturally occurring compounds, which possess a wide variety of biological activity including fungicidal and bactericidal properties . Starting from... 

Organic Materials. The sol-gel chemistry of organic materials is similar to that of inorganic materials. The first organic aerogel was prepared by the aqueous polyconclensation of resorcinol with formaldehyde using sodium carbonate as a base catalyst. 

In 1928, Schumm discovered that heating vinyl porphyrins in molten resorcinol resulted in facile loss of the vinyl groups from the porphyrins. It was subsequently shown that l -hydroxyalkyl, formyl and acetyl porphyrins behave similarly under the same conditions, i.e. these substituent groups also are removed. The Schumm devinylation reaction has been used in both synthetic and degradation studies on porphyrins, and it was stated in a paper in the Journal of Organic Chemistry that "One of the most useful reactions in the chemistry of natural porphyrins is the devinylation of vinyl porphyrins in molten resorcinol."... 

An interesting example of an application of this method pertains to the synthesis of pharmacologically active synthetic A1 -tetrahydrocannabinoids 134) of the type 267 which have a lipophilic tertiary alkyl side-chain. Equation 84 shows that organo-titanium chemistry provides a versatile means to prepare the precursors 264 (65-80 %)133). Demethylation of 264 using trimethylsilyl chloride and sodium iodide affords the resorcinol derivatives 265 ( 95%)133>. Compounds of this type have been previously condensed with 266 in the presence of acids to form the A1(6)-isomers of 267, which in turn can be converted into 267135). It should be mentioned that the meta-substitution pattern of 265 prohibits simple Friedel-Crafts alkylation of resorcinol, which is the reason why alternative multistep syntheses of 264 have had to be developed l34 136>. 

For the diazocoupling reaction with resorcinol and 4-nitrobenzene diazonium, see Coffey S, ed. Rodd s Chemistry of Carbon Compounds. Vol. 3, Part C. New York Elsevier Scientific, New York, 1973 136 and references cited therein. 

Hydroxyl radical generated from hydrogen peroxide in the presence of iron(II) salts hydroxylates most aromatic centres, and indeed a phenol hydroxylation process based on this chemistry was operated for nearly a decade.471 The process ran at similar conversions to the acid-catalysed route mentioned above, however selectivity to dihydroxybenzenes was somewhat lower, and some resorcinol was formed along with catechol and hydroquinone. 

Diisopropylbenzenes are valued precursors to subsequent oxidation products. For example, 1,3-Diisopropyl- and 1,4-diisopropylbenzenes are used via oxidation chemistry to produce the materials resorcinol and hydroquinone, respectively. 

Calixarenes are macrocyclic molecules synthesized with high yield by condensation of appropriate arenes and aldehyde derivatives. Calix means bowF in Latin and Greek, and this phrase reflects the shape of the tetramer, which usually adopts a bowl or beaker-like conformation. Gutsche first introduced the name calixarene for this class of compounds [38]. Several authors have exhaustively reviewed the chemistry and synthetic procedures, which lead to different structural modifications of calixarenes [39-42]. In general, three types of calixarenes derivatives are known first, metacyclophanes (type 1) second, those obtained by condensation of formaldehyde with phenol (type 11), and third, those obtained by reaction with resorcinol (type III) (Scheme 6). The latter modifications are also called resorcarenes to distinguish calixarenes of type III from those of type II. 

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