Abnormal products

However, in the reaction of 1-alkenylboranes with aryl- or 1-alkenyi iodides. 2-aryl-l-alkenes 648 are obtained as the main products. When Pd metal produced from Pd(OAc)2 as a catalyst and EtjN as a weak bu.se are u.sed. abnormal products are formed. On the other hand, normal products 649 are obtained by using NaOH[5l7]. 

Kharasch s earliest studies in this area were carried out in collab oration with graduate student Frank R Mayo Mayo performed over 400 experi ments in which allyl bromide (3 bromo 1 propene) was treated with hydrogen bromide under a variety of conditions and determined the distribution of the normal and abnormal products formed during the reaction What two prod ucts were formed Which is the product of addition in accordance with Markovmkovs rule Which one corresponds to addition opposite to the rule ... 

In some cases iinsaturated groups (carbon-carbon double bonds, carbonyl groups or nitriles) in close proximity to the carbon radical interact and give rise to abnormal products. Details will be discussed in the following sections. 

It is now thought140 that the abnormal product is formed reversibly from the... 

In the presence of Eu(fod)3 the endo-oycloadduct is the predominant reaction product in the presence of SnCl4 the abnormal product is predominant... 

Dichloroquinoxaline (178, R = Cl) gave an abnormal product, 3-dimethyl-amino-2-quinoxalinecarbonitrile (182) (CuCl, Me2NCHO, reflux, 8 h 51% presumably either Cl or CN was displaced by Me2NH from the solvent) 7 ... 

Ethers with an alkyl group in the y position (ArO—C—C—C—R systems) sometimes give abnormal products, with the (3 carbon becoming attached to the ring " ... 

It has been established that these abnormal products do not arise directly from the starting ether but are formed by a further rearrangement of the normal product ... 

This table indicates the chromosomal location of several genes and the diseases associated with deficient or abnormal production of the gene products. The chromosome involved is indicated by the first number or letter. The other numbers and letters refer to precise localizations, as defined in McKusick VA Mendelian Inheritance in Man, 6th ed. John Hopkins Univ Press, 1983. 

Multiple myeloma is a malignancy of plasma cells that is characterized by an abnormal production of a monoclonal protein. Features of the disease include bone lesions, anemia, and... 

The suggested fragments from (54a) are a carbonyl compound (58) and a peroxy zwitterion (59), the latter then effecting a 1,3-dipolar addition on the former to yield the ozonide (57a). Alternative reactions of the zwitterion (59), including its polymerisation, lead to the formation of the abnormal products that are sometimes observed in addition to the ozonide, If ozonolysis is carried out in MeOH as solvent then (59) is trapped , as it is formed, by its conversion into the relatively stable a-hydroperoxy ether (60) ... 

In addition to these interconversions, the metabolism of fat and the metabolism of carbohydrate are inseparably related. This fact is most clearly demonstrated by the appearance of such abnormal products of fat oxidation as the so-called ketone bodies in the blood and urine whenever the supply of carbohydrate is deficient or in cases where the organism is unable to metabolize this foodstuff. Whether ketonuria results because the metabolism of fat must occur concomitantly with that of D-glucose (ketolysis), or whether the presence of D-glucose prevents any fat breakdown because it is preferentially oxidized (antiketogenesis) is still a moot question. 

The formation of an intermediate with electron-deficient oxygen is also one of the possible paths for the oxidation of alcohols. An intermediate such as LVI, or the chromate ester LVII which might behave in similar fashion, could rearrange to give "abnormal products or lose a proton to give the usual, expected product.889-882... 

Cyclobutanones were found to be much more reactive under these conditions, presumably due to relief of ring strain (131). Racemic cyclobutanone (192) is oxidized under the conditions described above to provide lactones 193 and 194 in a ratio of 55 45, Eq. 111. The expected lactone product 193 is formed in 67% ee while the abnormal product 194 is formed in 92% ee. The major enantiomers of the two products are complementary, resulting from enantiomeric ketones. 

The attack of the nucleophile on the acceptor-substituted allene usually happens at the central sp-hybridized carbon atom. This holds true also if no nucleophilic addition but a nucleophilic substitution in terms of an SN2 reaction such as 181 — 182 occurs (Scheme 7.30) [245]. The addition of ethanol to the allene 183 is an exception [157]. In this case, the allene not only bears an acceptor but shows also the substructure of a vinyl ether. A change in the regioselectivity of the addition of nucleophilic compounds NuH to allenic esters can be effected by temporary introduction of a triphenylphosphonium group [246]. For instance, the ester 185 yields the phos-phonium salt 186, which may be converted further to the ether 187. Evidently, the triphenylphosphonium group induces an electrophilic character at the terminal carbon atom of 186 and this is used to produce 187, which is formally an abnormal product of the addition of methanol to the allene 185. This method of umpolung is also applicable to nucleophilic addition reactions to allenyl ketones in a modified procedure [246, 247]. 

Titanium tetrachloride promoted reactions of 1-methyl-1-trimethylsilylallene with qui-nones 25 afforded products derived from a reaction with one of the carbonyl groups on the quinones. Besides the substitution pattern on the allene, the higher activity of titanium tetrachloride has to be considered to play a role in this abnormal product formation. 

Maggi E Abnormal production of T-helper 2 cytokines interleukin-4 and interleukin-5 by T cells from newborns with atopic parents. Eur J Immunol 1996 26 2293-2298. 33... 

Dakin, H. D. West, R. J. Biol. Chem. 1928, 78, 91, 745, and 757. In 1928, Henry Dakin and Rudolf West, a clinician, reported on the reaction of a-amino acids with acetic anhydride to give a-acetamido ketones via azalactone intermediates. Interestingly, one year before this paper by Dakin and West, Levene and Steiger had observed both tyrosine and a-phenylananine gave abnormal products when acetylated under these conditions.Unfortunately, they were slow to identify the products and lost an opportunity to be immortalized by a name reaction. 

This equation reveals atypical product inhibition patterns for a random mechanism P is noncompetitive with both A and B Q is competitive with both A and B. Whenever abnormal product inhibition patterns are ob-... 

Conflicting results have been reported for the reaction of the manno epoxide with hydrochloric acid in acetone. Mukheijee and Srivastava100 claimed that approximately equal amounts of the normal and abnormal products are formed, whereas Newth and Homer 10 reported that 3-substitution (ratio 92 8) mainly occurs, as would be expected. Although the former workers claimed similar results for hydrobromic acid, their anomalous results need re-investigation. 

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