Methyl derivatives

Ihese relative probabilities can be easily determined by simply counting the number c imes during the simulation that the relevant value of lambda reaches unity. In the case ( the para-substituted benzamidines it was possible after only a relatively short simulatio (110 po) to observe that the p-chloro and p-methyl derivatives were significantly weaki than the p-amino and the parent compound (Figure 11.18). In this particular case, all foe... 

Substitution Derivatives of Ethyl Malonate, Ethyl malonate resembles ethyl acetoacetate in that it gives rise to mono- and di-substituted derivatives in precisely similar circumstances. Thus when ethanolic solutions of ethyl malonate and of sodium ethoxide are mixed, the sodium derivative (A) of the enol form is produced in solution. On boiling this solution with an alkyl halide, e.g, methyl iodide, the methyl derivative (B) of the keto form is obtained. When this is treated again in ethanolic solution with sodium ethoxide, the... 

By oxidation of the methyl derivative of an aromatic hydrocarbon with a solution of chromic anhydride in acetic anhydride and acetic acid. The aldehyde formed is immediately converted into the (/m-diacetate, which is stable to oxidation. The diacetate is collected and hydrolysed with sulphuric acid, for example ... 

The reactivity of sulfathiazoles has been reviewed (65). Methylation in alkaline solution with dimethyl sulfate gives only the ring methylated derivative (85). Mixtures of products are obtained with diazomethane as alkylating agent (see p. 37). Other alkyl halides in aqueous alkali lead also to ring-alkylated products (85. 251, 650. 669-671). 

Alkoxy and 2-methyl derivatives of A-2-thiazoline-4-one (182) react with phosphorus oxychloride to yield the thiazolylphosphoric esters (183), which have insecticidal uses (Scheme 95) (428-430). 

Amino-A.-selenazoline and its 5-methyl derivative have previously been obtained by Baringer (61) starting from 2-bromoethylamine hydrobromide and l-amino-2-bromopropane hydrobromide, respectively, by reaction with potassium selenocyanate. 

The first empirical and qualitative approach to the electronic structure of thiazole appeared in 1931 in a paper entitled Aspects of the chemistry of the thiazole group (115). In this historical review. Hunter showed the technical importance of the group, especially of the benzothiazole derivatives, and correlated the observed reactivity with the mobility of the electronic system. In 1943, Jensen et al. (116) explained the low value observed for the dipole moment of thiazole (1.64D in benzene) by the small contribution of the polar-limiting structures and thus by an essentially dienic character of the v system of thiazole. The first theoretical calculation of the electronic structure of thiazole. benzothiazole, and their methyl derivatives was performed by Pullman and Metzger using the Huckel method (5, 6, 8). 

Quantum chemistry methods allow the prediction of the ultraviolet transitions in good agreement with the experimental values in the case of thiazole and its three methyl derivatives (Table 1-18). A very weak absorption has been indicated at 269.5 nm that could correspond to an n- TT transition given by calculation at 281.5 nm (133). Ultraviolet absorption spectroscopy has been investigated in connection with steric interactions in the A-4-thiazoline-2-thione (74) series (181). It was earlier demonstrated by NMR technique that 4-alkyl-3 isopropyl-A-4-thiazoline-2-thiones exist in solution as equilibrium mixtures of two conformers (75 and 76), the relative populations of which vary with the size of R4 (182) for R4 = rBu the population of rotamer A is 100%, whereas for R4 = Me it is only 28%. Starting from the observed absorption wavelength for... 

COMPARISON OF ULTRAVIOLET ABSORPTION SPECTRA OF THIAZOLE AND HS METHYL DERIVATIVES WITH CALCULATED VALUES OF TRANSITIONS BY DIFFERENT METHODS... 

The spectra of substituted thiazole derivatives, especially the methyl derivatives, can be used to determine harmonic and combination bands of the T(ch) modes 27(c.,h> T(c.hi + T[Pg.351]

It is possible that for the methyl derivatives of thiazole the variable frequencies of the series V and VI correspond to the modes resulting from a coupling of the V(c-ch,) vibration with the vibration in the case of 2- or 5-substituted derivatives and with the vibration in the case of 4-substituted derivatives (99). 

The effect of alkyl groups in the 5-position on the reactivity of the thiazole nitrogen is analogous to that found for 3-alkylpyridines, in other words, a simple inductive effect. In passing from the unsubstituted heterocycle to the methyl derivative, the rate constant doubles a further increase in substitution produces a much less pronounced variation. 

In the same way, 4-cyanothiazole is obtained from the action of a mixture of Nj/NO on the methyl derivative at 500°C with Re catalysts (Scheme 22) (95). 

Selenium dioxide oxidation of methyl derivatives (Scheme 30). 

Compounds related to benzene were obtained from similar plant extracts Eor example a pleasant smelling resin known as tolu balsam was obtained from the South American tolu tree In the 1840s it was discovered that distillation of tolu balsam gave a methyl derivative of benzene which not surprisingly came to be named... 

Whereas the particular methylated derivative of laudanasoline (77, R = H) called (—)-reticii1ine (85) (59) gives rise to thebaine (84), codeiae (2,... 

Fig. 3. Oxidative coupling products of methylated derivatives of laudanosoline (77, R = H). See Table 8.

The methylphosphonates differ from the phosphodiesters and phosphorothiolates in that the methyl derivatives are uncharged and are thus less water soluble. Moreover, compared to the naturally occurring phosphodiesters, the methylphosphonates form slightly less stable duplexes with complementary DNA and RNA sequences. This effect has been ascribed to the iaevitable chiraUty problem that is, if one isomer biads less well, the overall binding is decreased. Methylphosphonates can enter cell membranes by a passive mechanism and are completely resistant to nucleases. 

In addition to the ahphatic (chain) molecules, the saturates contain cycloalkanes, called naphthenes, having mainly five or six carbons in the ring (Fig. 5). Methyl derivatives of cyclopentane and cyclohexane ate commonly found in greater quantity than the parent unsubstituted stmctures and can be present at levels above 2% (2). Fused-ting dicycloalkanes such as decahydronaphthalenes (decalins) and hexahydroindans are also common, but nonfused bicyhc naphthenes, eg, cyclohexyl cyclohexane, are not. 

Mixtures of /V-alkylanilines can usually be separated by fractional distillation. Mixtures of the methyl or ethyl derivatives have also reportedly been separated by converting the V/-ethyl or the /V-methyl derivative to the nonvolatile salt with -toluenesulfonic acid (12) or phthaUc anhydride (13), followed by distillation. 

Pyridine and its methyl derivatives, (2), (3), and (4), undergo amination with sodium amide at the 2-position eg, 2-anTino-3-methylpyridine [1603-40-3] and 2-anTino-5-methylpyridine [1603-41 -4] from (3) (eq. 3). This Chichibabin reactionis most important for introduction of a 2-amino substituent, which may be replaced readily by many other groups (18). 

Hydroxyisoquinolines. Hydroxy groups in the 5-, 6-, 7-, and 8-position show phenoHc reactions for example, the Bucherer reaction leads to the corresponding anainoisoquinolines. Other typical reactions include the Mannich condensation, azo-coupling reactions, and nitrosation. Both 0-methyl and /V-methyl derivatives are obtained from the methylation of 1-hydroxyisoquinoline, indicating that both tautomeric forms are present. Distillation of various hydroxy compounds, eg, 1- and 4-hydroxyisoquinoline, with zinc dust removes the oxygen. Treatment of 1-isoquinolinol with phosphoms tribromide yields 1-bromoisoquinoline [1532-71 -4] (178). 

The alkyl group also produces subde changes in the processing of the PVC, the use level and cost of the stabilizer, and in some cases even the final properties of the article, especially the heat distortion temperature or Vicat softening point. Overall, methyl derivatives are most widely used. Butyls are second and octyls a distant third. 

Bromothiophenes are toxic materials by aU routes. Inhalation toxicity of 2-bromothiophene is significant. Ecotoxicity is also noted for these materials, particularly for 2-bromo-3-methylthiophene. 2-Thiophenecarboxaldehyde and the 3-methyl derivative can cause minor irritation to the skin and eyes of rabbits. The former is a sensitizer to guinea pig skin, the latter is not. 2-Acetylthiophene is toxic in aU modes of contact. Severe exposure causes serious inflammation of the lung, damage to many organs, and depression of the central nervous system. 

Vinyl chloride forms a photo [2 + 2] cycloadduct with 1-isoquinolone [491-30-5] and its /V-methyl derivative (57). 

Methylcoumaria [2445-82-1] and 6-methylcoumarin [92-48-8] h.2ive some use in the perfume iadustry. The 6-methyl derivative is permitted in flavor compositions. 

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