Sodium methyl derivatives

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... 

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). 

Both the 4- (38) and 6-(31) nitrimines are reduced with sodium boro-hydride to the corresponding y5-nitramine derivatives, e.g., (41)], which are methylated with methyl iodide and potassium carbonate. The A -methyl derivative is reduced in modest yield to the 5a-fluoride (43) with lithium aluminum hydride. 

The sodium or potassium salt of 6-azauracil in aqueous ethanol, anhydrous ethanol, or ethylene glycol reacted with methyl iodide practically exclusively to give the 3-methyl derivative (63). In toluene the sodium, potassium, and mercuric salts produced no methylated derivatives whereas the silver salt also yielded the 3-methyl derivative, Similarly, the 3-methyl derivative was prepared from the mercuric salt of 6-azathymine, and its structure was established by hydrolysis to pyruvic acid 4-methylthiosemicarbazone. ... 

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. ... 

Sodium methyl mercaptide in xylene was reported to react (25°, 2 hr) in a stepwise fashion with 3,5-dichloro-as-triazine to yield the 3-methylthio-5-chloro and then (70°, 2 hr) the 3,5-bis-methylthio derivatives. However, the structure of the former is very likely to be 307. With dimethylamine in benzene (25°, 5 min), ethyleneimine in ether (25°, 3 min), and alcoholic ammonia (25°, few min), this dichloro derivative was assumed to form 3-amino derivatives. The high reactivity of as-triazines is demonstrated by the facile ethoxylation... 

The ultraviolet and infrared spectra of 2-aminothiazole and the methyl derivatives of both the imino and the amino forms have been compared and discussed by Sheinker, Kushkin, and Postovskii ° who showed that the amino form predominates in the solid state and in various solvents. The reaction of 2-aminothiazoles with methyl iodide in the presence or in the absence of sodium ethoxide has been considered to give information concerning the proportion of the amino and imino forms present under these conditions, ... 

Polyacrylamide may be converted into a sulfo-methyl derivative by condensation with formaldehyde and sodium bisulfite under basic conditions. 

The benzothiazepinone 2 is converted into the Ar-methyl derivative 5 by treating its sodium salt with iodomethane and into 5-methoxy-l,4-benzothiazepine (6) with trimethyloxonium tet-rafluoroborate. Compound 6 gives the S-methyl salt 7 on methylation with iodomethanc/sil-ver(I) tetrafluoroborate.49... 

Methylation of the 6,7-dimethyl derivative of 133 with methyl iodide in sodium hydroxide or sodium ethoxide gave two S,N-dimethyl derivatives, whereas in sodamide or ammonia, only the 5-methyl derivative was obtained. Methylation with diazomethane gave four methyl derivatives and with methyl chloride two di-jV-methyl and one 5,/V-dimethy] derivative were obtained (80H1139). Methylation of 153, obtained from 152, gave 4-methyl-3-methylthio-triazinoindole 155, whose hydrolysis or oxidation gave 154 (76T1735). On the other hand, methylation of 156 gave methiodide... 

Much more promising is the method of Schechter and Haller (3), which depends upon the coupling of the tetranitro derivative of DDT with methanolic sodium methylate. Under conditions of intensive nitration methoxychlor will yield by this procedure a red color with an absorption maximum at 535 m/z. 

The addition product of sodium and pyridine (or its 2-methyl derivative) ignites in air. 

It was found possible to saponify ovomucoid with sodium hydroxide and to methylate simultaneously with methyl Bulfate, the carbohydrate residue thereby forming an N-acetyl methyl derivative.14 Hydrolysis of this material yielded N-acetyl-3,4,6-trimethyl-D-glucosamine (7 moles) (LIVJ, D-mannopyranose (2 moles) (LV), 3,4,6-trimethyl-D-mannopy-ranose (1 mole) (LVI), and tetramethyl-D-galactopyranose (1 mole) (LVII). 

Haworth, Hirst and Percival23 methylated inulin by first acetylating and subsequently converting the acetate to the methyl derivative by means of dimethyl sulfate and sodium hydroxide in acetone solution, a procedure described by Haworth and Streight.24 They hydrolyzed trimethylinulin and quantitatively determined the amounts of trimethyl-D-fructose and tetramethyl-D-fructose formed. There was obtained 3.7%... 

The acetate was dissolved in acetone and converted to the methyl derivative by the use of dimethyl sulfate and sodium hydroxide. After three methylations, a product containing 45.6% OCHa was obtained. Hydrolysis yielded dimethyl-, trimethyl-, and tetramethyl-D-fructose in the ratios (calculated as D-fructose) of 1 8 1. The trimethyl-D-fructose... 

Alkylation or acylation takes place at the nitrogen in position 1 when l/7-[l,2,4]triazolo[4,3-A][l,2,4]triazole 9 is treated with methyl iodide or acetyl chloride, furnishing compound 10 or 11, respectively <1983S415>. The 7-methyl isomers 13 are obtained after conversion of compounds 9 into the 1-acetyl derivatives 11 followed by methylation with methyl trifluoromethanesulfonate to give the l-acetyl-6-aryl-7-methyl-3-methylthio-17/-[l,2,4]triazolo[4,3-A]-[l,2,4]triazol-7-ium-trifluoromethanesulfonates 12, which upon treatment with aqueous sodium carbonate afford the 7-methyl derivatives 13 <1985BCJ735>. 

On methylation of the disaccharide with dimethyl sulfate and sodium hydroxide a hexamethyl ether of the carbohydrate was obtained. When this fully methylated derivative (VII) was hydrolyzed with acid, 2,3,4,6-tetramethyl-D-glucose (VIII) and dimethyl-L-arabinose (IX) were produced. Since position 3 in the L-arabinose component of VI was shown to be occupied in glycosidic linkage with D-glucose, the dimethyl-L-arabinose could be either the 2,5- or 2,4-dimethyl derivative (IX),... 

Ethynylallenes [35], the didehydro analogs of vinylallenes, have also been known for some time, the parent system 7 having been obtained in 1960 by reduction of 3-chloro-l,4-pentadiyne (101) with zinc-copper couple in butanol [36] and the 5-methyl derivative 103 by base-catalyzed isomerization of 1,4-hexadiyne (102) with sodium ethoxide in ethanol (Scheme 5.13) [9]. 

Scheme 6.113 Formation of heptafulvalene (522), its methyl derivative 556 and its dimethyl derivatives 557 on co-thermolysis of the sodium salts of benzaldehyde and p-methylbenzaldehyde tosylhydrazones.

FIGURE 8.16 Preparation of Cbz/Boc-/V-methylamino acids by methylation of Cbz/Boc-amino acids. [Benoiton et al., 1972]. Sodium hydride is added to substrate and methyl iodide in tetrahydrofuran, producing the sodium salt of the /V-methylated derivative. 

The treatment of the diethyl aminomethylenemalonate derivative (1427, R = Et) in methanol in the presence of sodium methylate under reflux for 2 hr gave the dimethyl ester (1427, R = Me) in 85% yield (78GEP2747199 82SZP627755). 

N-(l-Methyl- and l-benzyl-3-pyrrolyl)aminomethylenemalonates (1476, R = Me, CH2Ph) were obtained in 91% and 91% yields, respectively, when 3-pyrrolylaminomethylenemalonate (1476, R = H) was reacted with methyl iodide or with benzyl bromide in DMF in the presence of sodium methylate at ambient temperature for 10-60 min (85JHC83 89JHC1029). N-Methyl derivatives (1477) were prepared in nearly quantitative yield under the previous conditions with methyl iodide if the reaction mixtures were stirred overnight. 

Isopropylidene N-substituted aminomethylenemalonates (442, R1 = R2 = Me) were methylated with methyl iodide in dimethyl sulfoxide in the presence of sodium hydride at room temperature overnight to give the N-methyl derivatives (1615) in 56-90% yields [88JCS(P )863,88JCS(P2)759]. 

---