Dialkyl Sulfates Research Articles

STUDIES ON SEVEN-MEMBERED RING COMPOUNDS. XV. PREPARATIONS OF TROPONEIMINE DERIVATIVES.

Reactions between 2-aminotropone derivatives and dialkyl sulfates were examined. Methylation sodium salt of 2-aminotropone with dimethyl sulfate resulted in N-methylation yielding 2-methylaminotropone (III). On the other hand, the direct methylation of 2-aminotropone (I) with dimethyl sulfate resulted in O-methylation yielding 2-methoxytroponeimine (V). Troponeimines listed in Table I were prepared by the direct alkylation of 2-aminotropone derivatives with dialkyl sulfates. In these preparations, sulfonates listed in Table II were also obtained.

Studies on the Azaindolizine Compounds. XIII. Alkylation of 5-Methyl-s-triazolo [1, 5-a] pyrimidin-7-ol.

The alkylation of 5-methyl-s-triazolo [1, 5-a] pyrimidin-7-ol (I) with alkyl iodide and dialkyl sulfate always afforded the two N-alkylated products (IIa-b and IIIa-b). The structure of these products was established to be 4-alkayl-5-methyl-s-triazolo [1, 5-a]-pyrimidin-7 (4H)-ones and 3-alkyl-5-methyl-s-triazolo [1, 5-a] pyrimidin-7 (3H)-ones respectively.

Heilmittelchemische Studien in der heterocyclischen Reihe. 33. Mitteilung. Pyridazine XII. Über 1‐Aryl‐2‐alkyl‐3,6‐dioxo‐1,2,3,6‐tetrahydro‐pyridazine

AbstractSeveral 1,2‐disubstituted 3,6‐dioxo‐1,2,3,6‐tetrahydro‐pyridazines have been prepared. Direct alkylation of 1‐aryl‐3‐hydroxy‐6‐oxo‐1,6‐dihydro‐pyridazines with dialkyl sulfates is shown to give either 1‐aryl‐2‐alkyl‐3,6‐dioxo‐1,2,3,6‐tetrahydro‐pyridazines or a mixture of these with 1‐aryl‐3‐alkoxy‐6‐oxo‐1,6‐dihydro‐pyridazines.

The sulphation reaction between aqueous sulphuric acid and α‐olefins

AbstractThe initially heterogeneous reactions between 75 to 85% w/w aqueous H2SO4 and hexene‐1, heptene‐1, octene‐1, and decene‐1, have been investigated as a necessary preliminary to the estimation of the heat associated with the production of the monoalkyl sulphates. The effects of different proportions of acid and olefin, the aqueous concentration of the acid, the temperature and the speed of stirring, were examined.At room temperatures, the reaction products isolated with a high ratio of 80% w/w acid to olefin, were substantially the secondary monoalkyl sulphates and their corresponding alcohols. Under these conditions the formation of the dialkyl sulphates and polymers was avoided.It was found possible to represent approximately the results in terms of a two‐stage consecutive reaction. RCH : CH2 → RCH(O·SO3H)‐CH3 → RCH(OH2+)·CH3The reactions were shown in each case to be of the second order depending upon some function of the concentration of the aqueous H2SO4. The observed kinetics were shown to be in agreement with the formation of a carbonium‐ion intermediate.

Pyrimidine誘導体の合成研究 (第7報)

It had earlier been reported that the alkylation of 2-sodioformyl-3-alkoxypropionitrile (II or III) with dialkyl sulfate afforded cis- and trans-2-alkoxymethylene-3-alkoxypropionitrile (IV, V, and VI) but later examinations revealed that the substances obtained in this reaction were still impure. Further purifications showed that besides the cis and trans isomers of the foregoing nitriles, another isomer of low boiling point has been formed. This new isomer was found to have C=C bond from the Raman spectra although this point was not clear from its infrared spectrum. Ozonolysis of this isomer afforded formaldehyde, proving the presence of endo-methylene group. Catalytic reduction resulted in the rapid absorption of one mole of hydrogen to form 2-dialkoxymethyl-propionitrile (X and XI). The latter was confirmed from its infrared spectrum and formation of 2, 5-dimethyl-4-aminopyrimidine (XII) by condensation with acetamidine. These experimental results have proved that the new-type isomer obtained by the foregoing reaction is 2-dialkoxymethyl-acrylonitrile (VII, VIII, and IX).

チアゾール誘導体の合成研究 (第3報)

By the alkylation of 2-mercapto-4-methyl-5-β-hydroxy (or acetoxy) ethylthiazole (I or IV) with alkyl halides or dialkyl sulfates, corresponding alkylthio compounds (III or V) were prepared. Their reduction and desulfurization with aluminum amalgam or zinc dust afforded 4-methyl-5-β-hydroxy (or acetoxy) ethylthiazole (II or VII) in a good yield. The basicity of alkylthio compounds (III) decreases as the alkyl group becomes larger, with increased resistance to reduction. The benzylthio compound forms toluene and 2-mercapto-4-methyl-5-β-hydroxyethylthiazole by the reduction, and benzyl alcohol and 4-methyl-5-β-hydroxyethylthiazole by oxidation with hydrogen peroxide, differing in properties from those of the lower alkylthio compounds described above.

The Reaction of Dialkyl Sulfates with ROMgBr Compounds

The Reaction of Dialkyl Sulfates with ROMgBr Compounds