P N-methyl

Cfl 6H3 4CIN10 f 1-Methyl-3,3-dimethyl-2-((p-N-methyl-N-/3-chloroethyl-amino)styryl)indole bis(7,7,8,8-tetracyanoquinodimethane), 39B, 466 Ca8H26Ni f lf1 -Dimethyl-4,4 -bipyridyliurn 7,7,8,8-tetracyano-p-quinodimethanide, 45B, 682... 

Methylaniline Ethylaniline n-Propylaniline n-Butylaniline Benzylaniline 2 -MethyIbenzylamine N-Ethylbenzylamine 2 -Methyl o-toluidine N-Methyl m-toluidine 2 -MethyI p-toluidine N-Ethyl o-toIuidine N-Ethyl m-toIuidine 2S -Ethyl p-toluidine 2 -MethyI a-naphthylamine N-Methyl p-naphthylamine N-Phenyl- a-naphthylamine 2 -Phenyl-P-naphthylamine... 

The influence of a large number of oc-amino acids on the values of and k at have been determined. These a-amino acids included glycine, L-valine, L-leucine, L-phenylalanine, L-tyrosine, L-tryptophan, NOrmethyl-L-tryptophan (L-abrine), N-methyl-L-tyrosine, N,N-dimethyl-L-tyrosine and p -me thoxy-N-me thyl -L -phenyl al anine. 

The reaction of N-methyl-(p-dimethylamino)thiobenzamide (99) with a number of a-haloketones and a-bromoheptaldehyde gave stable 4-hydroxythiazolinium salts (100), which could be subsequently dehydrated by methanolic hydrogen chloride to the thiazolium salts (101), (Scheme 44) (622). 

Various 4-, 5-, or 4,5-disubstituted 2-aryIamino thiazoles (124), R, = QH4R with R = 0-, m-, or p-Me, HO C, Cl, Br, H N, NHAc, NR2, OH, OR, or OjN, were obtained by condensing the corresponding N-arylthiourea with chloroacetone (81, 86, 423), dichloroacetone (510, 618), phenacyichloride or its p-substituted methyl, f-butyl, n-dodecyl or undecyl (653), or 2-chlorocyclohexanone (653) (Method A) or with 2-butanone (423), acetophenone or its p-substituted derivatives (399, 439), ethyl acetate (400), ethyl acetyl propionate (621), a- or 3-unsaturated ketones (691), benzylidene acetone, furfurylidene acetone, and mesityl oxide in the presence of Btj or Ij as condensing agent (Method B) (Table 11-17). 

Applications. Polymers with small alkyl substituents, particularly (13), are ideal candidates for elastomer formulation because of quite low temperature flexibiUty, hydrolytic and chemical stabiUty, and high temperature stabiUty. The abiUty to readily incorporate other substituents (ia addition to methyl), particularly vinyl groups, should provide for conventional cure sites. In light of the biocompatibiUty of polysdoxanes and P—O- and P—N-substituted polyphosphazenes, poly(alkyl/arylphosphazenes) are also likely to be biocompatible polymers. Therefore, biomedical appHcations can also be envisaged for (3). A third potential appHcation is ia the area of soHd-state batteries. The first steps toward ionic conductivity have been observed with polymers (13) and (15) using lithium and silver salts (78). 

CHgO)2. CgH2(CHO). CH2. CH2. NMc2, which is N-methyl-hydrastinine (p. 165), in which a methylenedioxy group has been replaced by two methoxyl groups. 

C(O.Me). N(i>) — CO N(6)Me, the N-methyl base, C22H24O3N2, so produced becoming available as the methiodide as isolated. Part of the original p eiidostrychnine methyl ether methiodide was also believed to undergo hydrolysis thus —... 

Although trans epoxides ean be obtained via epoxidation of aeyelie cti-eonjugated olefins under speeified eonditions, a direet method based on the epoxidation of trans-olefins would be valuable. The Katsuki group reeently identified eatalyst 15 as an effieient catalyst for the direet epoxidation of trans-olefins. Crucial to the sueeess of the eatalyst is the inherent adoption of a deeply folded eonformation eoupled with the use of ehlorobenzene as solvent. While only a limited number of substrates have been examined to date using catalyst 15, the results are very promising. For example, trans- -methyl styrene is epoxidized in 91% ee, trans-P-n-butyl styrene in 95% ee, and trans-stilbene in 87% ee. 

Alkylation at the ind-N of l,2,3,4-tetrahydro-j8-carbolines has been carried out with alkyl halide after treatment with sodamide in the usual manner. Cyanoethylation of a p /r-V-substituted tetrahydro-jS-carboline in the presence of Triton B yields the corresponding 9-cyanoethyl derivative. Similarly, treatment of p / -V-methyl-l,2,3,4,4a,9b-hexahydro-y-carboline with sodamide, followed by benzyl chloride, leads to the ind-A -benzyl-substituted derivatives. l-Oxo-l,2,3,4-tetrahydro-j8-carboline yields the ind-A -methyl derivative directly with dimethyl sulfate.Prolonged treatment with sodium hydride, followed by methyl iodide, yields the 2,9-dimethyl derivative. Heating with sodium hydride in acetone followed by the addition of dimethyl sulfate gives rise to the ind-V-methyl derivative. ... 

Complexes 79 show several types of chemical reactions (87CCR229). Nucleophilic addition may proceed at the C2 and S atoms. In excess potassium cyanide, 79 (R = R = R" = R = H) forms mainly the allyl sulfide complex 82 (R = H, Nu = CN) (84JA2901). The reaction of sodium methylate, phenyl-, and 2-thienyllithium with 79 (R = R = r" = R = H) follows the same route. The fragment consisting of three coplanar carbon atoms is described as the allyl system over which the Tr-electron density is delocalized. The sulfur atom may participate in delocalization to some extent. Complex 82 (R = H, Nu = CN) may be proto-nated by hydrochloric acid to yield the product where the 2-cyanothiophene has been converted into 2,3-dihydro-2-cyanothiophene. The initial thiophene complex 79 (R = R = r" = R = H) reacts reversibly with tri-n-butylphosphine followed by the formation of 82 [R = H, Nu = P(n-Bu)3]. Less basic phosphines, such as methyldiphenylphosphine, add with much greater difficulty. The reaction of 79 (r2 = r3 = r4 = r5 = h) with the hydride anion [BH4, HFe(CO)4, HW(CO)J] followed by the formation of 82 (R = Nu, H) has also been studied in detail. When the hydride anion originates from HFe(CO)4, the process is complicated by the formation of side products 83 and 84. The 2-methylthiophene complex 79... 

In a more general approach toward pentacyclic heteroaromatics from tricyclic ketones, treatment of the N-methylated derivative of 112 with p-tolylhydrazine, followed by Fischer indolization of the resulting phenylhydrazone in a mixture of trifluoroacetic acid and acetic acid, produced only a low yield of 114, although this method proved to be considerably mrae efficient for synthesis of analogous systems containing other heteroatoms than nitrogen (98SC1239). 

Acylation of ami noketone 8 with the acid chloride from p-toluic acid affords the corresponding ester (10) catalytic hydrogenation leads to the bronchodilator bitolerol (11). An analogous scheme starting from the N-methyl ketone (12) and pivaloyl chloride gives ami noalcohol (14). This compound is then resolved to isolate the levorotatory isomer. There is thus obtained the drug dipivefrin. 

Cyclohexanecarbonyl chloride EK Triethylamine MCB, EK N-Methyl-A -nitroso-p-toluenesulfonamide A Isophorone MCB, A d < -Octalone-2 (Chapter 9, Section III)... 

A mixture of 17.6 grams of p-n-butoxyacetophenone, 12.1 grams of piperidine hydrochloride, 4.5 grams paraformaldehyde, 0.25 cc concentrated hydrochloric acid, 52.5 cc nitro-ethane, 7.5 cc of 95% ethanol, and 15 cc of toluene was boiled under reflux for one hour, removing water formed in the reaction by means of a condensate trap. The mixture was then cooled. The crystals which formed were collected by filtration, washed with anhydrous ether and recrystallized from methyl ethyl ketone. The crystals thus obtained, which melted at 174°-175°C, were shown by analysis to be 4-n-butoxy-beta-piperidinopropiophen-one hydrochloride. 

Poly(N-methyl- 2-vinylpyr inium bromide) (p(2-VPMeBr) ]... 

The typical systems are BPO-DHET(N,N-di(2-hy-droxyethyl)-p-toluidine) system, BPO-DHPT(N,N-di(2-hydroxypropyl)-p-toluidine) system, BPO-HMA(N-2-hydroxyethyl-N-methyl-aniline), and BPO-HMT(N-2-hydroxylethyl-N-methyl-p-toluidine) system [17-19]. Their polymerization rate and overall activation energies of polymerization Ea are determined and the data are compiled in Table 2. 

Similar results were obtained in the photografting reaction of N-methyloyloxethyl-N-methyl-p-toluidine... 

---