Ullmann’s reaction

Mix I gram of phenol with i c.c. of dimethyl sulphate and add 4 c.c. of a lo per cent, solution of caustic soda. Warm and shake. The odour of phenol is replaced by that of anisole, which can be extracted from the licjuid by ether (Ullmann s reaction). See Appendix. p. 294. 

A STM-induced Ullmann s reaction between two molecules has also become possible as demonstrated for CeHsI on Cu(lll), producing a single biphenyl molecule (Hla et al, 2000). Here A is used to dissociate the CeHsI molecule into... 

Variations of Ullmann s reaction conditions have been reported by Denny and co-workers, who successfully applied anhydrous conditions implying CuCl/Cu, AA-alkylmorpholine as a base, and high-boiling solvents such as butanediol. This method was generally high-yielding except for very electron-deficient amines (8-aminoisoquinoline) or sterically hindered anilines (e.g., 2-chloro-6-fluoro-aniline). In some cases, copper catalysis led to disubstitution (2,6-dichloroaniline) ° or had no effect on yields or reactivity these couplings were carried out in the absence of metal catalyst. 

Westerterp KR, Wammes WJA. Three-phase trickle-bed reactors. In Ullmann s reaction engineermg. Weinheim Wiley-VCH 2013. p. 651-663. 

Reaction of bisphenol with chloronitroaromatic compounds was generally performed in dimethylformamide (DMF) or dimethyl sulfoxide (DMSO) at reflux using K2C03 as a base.108 109 It is possible to achieve this condensation in Ullmann s conditions by using a cuprous chloride or iodide-pyridine system as a catalyst when this reaction is performed with deactivated aromatic compounds, it gives too poor yields110 ultrasounds can dramatically improve yields without solvent.111... 

When subjected to Ullmann biaryl reactions, 8-bromo-l-oxazolinylnaph-thalene (,S)-27 can be converted to the 8,8 -substituted binaphthyl 28 in high diastereomeric excess (another isomer, the (a/ ,b )-diastcrcomer, is less than 3%).40... 

N-arylation has been used as the first step in several syntheses of complex molecules. The Ullmann-type reaction of 2-iodo-3-methoxybenzoic acid with l-methylpiperazine-2,5-dione forms the basis of Kishi s total synthesis of dehydrogliotoxin (81T2045) (Scheme 12). 

The enantiomerically pure bridged biphenyl, (—)-(R)-3,9-bis[4-(dodecyloxy)benzoyloxy]-5,7-dihydro-l,ll-dimethyl-dibenzo[c,( ]thiepine 80, was prepared from enantiomerically pure diiodide 197 (Scheme 25) <1998JOC3895>. The synthesis of the precursor 197 was based on Ullmann coupling reaction of the chiral oxazoline (-)-(S)-195. 

Fig 22.10. Reaction rate for NH3 synthesis. Dependence on the ammonia concentration at various pressures. (Courtesy of Wiley-VCH. Bakemeier, H., Huberich,T, et. al. "Ammonia" in Ullmann s Encyclopedia of Industrial Chemistry, 5th Ed., Vol. A 2, VCH Verlagsgesellschaft, Weinheim 1985, pp. 143-242. 

Westerterp, K.R., Wijngaarden, R.J., Principles of Chemical Reaction Engineering and Plant Design, Ullmann s Encyclopedia of Industrial Chemistry (1992) Vol. B4 (5th edn.). Weinheim VCH. 

For a more detailed treatment refer to textbooks about chemical reaction engineering, such as M. Baems, H. Hofmann, A. Renken, Chemische Reaktionstechnik, 2nd ed., Thieme, Stuttgart, 1992 K. R. Westerterp, R. J. Wijngaarden, Ullmann s Encycl. Ind. Chem. 5th ed. 1992, Vol. B4, pp. 5-83 and following chapters. 

Phenols are generally etherified by Ullmann s method,684-686 reaction occurring in two stages ... 

The Ullmann coupling [30] involves treatment of aryl halides with stoichiometric copper at high temperatures to yield biaryl compounds. Considerable effort has been made to lower the temperature necessary for initiation of the reaction, as well as decrease the required amount of copper salts. These advances served as the basis for extending this method for the synthesis of aryl heteroatom bonds, known as the Ullmann Condensation Reaction [22, 31, 32]. After several reports for C-O and C-N bond formation, methods for C-S bond formation began to emerge. 

Since articles in the encyclopedias of general knowledge as well as in the technical encylopedias are written by specialists, one may find authoritative information in those works, though an oblique approach may be needed in order to find some subjects. Thus, Ullmann s Encykhpddie der technischen Chemie relates detailed information on the metallurgical and other commercial uses of the thermite reaction under Aluminothermie (Vol. 1) and treats the subject of fireworks rather extensively under Pyrotechnik (Vol. 14). This edition has not as yet (1966) reached its final volume, which will contain the subject of matches under Ziindwaren. 

HLAVACEK V., PUSZYNSKI J.A., VILJOEN H.J., GATICA J.E., Model Reactors and their Design Equations, Ullmann s Enc. Ind. Chem., vol. B 4, 121 (1995). LEVENSPIEL O., Chemical Reaction Engineering, Wiley (1972). 

Transition metal-catalyzed esterification, includinglactonization 12SL357. Copper-catalyzed reactions of diazo compounds 12CC10162. Synthetic developments and applications of Ullmann-type reactions (formation of C—O, C—N, or C—S bonds) 130PP341. 

At the beginning of 20 century, Fritz Ullmann reported copper-mediated coupling reactions of aryl halides. The formation of biaryls from the reductive coupling of two aryl halides using stoichiometric amounts of copper was the first type of coupling reported by Ullmann s laboratory (Equation 19.91). Two years later, Ullmann reported that stoichiometric amounts of copper compounds mediate the ipso-substitu-tion of an aryl halide by heteroatom nucleophiles, such as phenoxides and arylamines... 

Ueda and co-workers [183] synthesized poly-(phenylene ether)s with pendant perfluoroal-kyl sulfonic acid groups with lEC values of 1.17-1.83 mEq./g by nucleophilic polycondensahon reachon of a perhuoromonomer such as decafluo-robiphenyl or hexahuorobenzene with 2,5-bisip-iodophenyl)hydroquinone, followed by the Ullmann coupling reaction with potassium 1,1,2,2-tetrafluoro... 

At elevated temperatures, oxygen reacts with sodium cyanide to yield nitrogen, carbonate, and carbon dioxide according to the two-step reaction (Ullmann s, 1987) ... 

Sulfuric acid reacts with sodium cyanide aeeording to the reaction Ullmann s, 1987) 2NaCN + H2SO4 Na2S04 + 2HCN (39.24)... 

Analytical chemistry in these early decades was often accorded the secondary status of a faithful servant, but even the few examples cited here demonstrate quite convincingly that it also pursued its own unique set of principles—and for its own. sake, with a strictly scientific orientation. The principles themselves were shaped by Berzelius and Wohler experiment rather than theoretical speculation was the starting point and source of inspiration in this era characterized largely by chemical reactions. Readers of the present essay should in fact take the time to examine the third edition of Ullmann s (12] and discover there what the expression analytical procedure actually meant even as late as the end of World War II. There can be no mistaking the fact that purely chemical methods were still domi-... 

Many times, the conversion of a reactor depends on the operating temperature. Even if isothermal operation is recommended, sometimes it is not easy to remove the energy generated during the reaction, or because it can be an asset for the process, the reactor operates under adiabatic conditions. The example that we are trying to solve now presents the features of this last type. In the production of nitric acid from ammonia, the converter oxidizes NHj into NO. The conversion of that reactor varies with temperature and the conversion profile may be obtained from experimental data in the Ullmann s Encyclopedia [9]. 

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