- Aminomethylation of tocopherols
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A process for the production of a Mannich reagent comprises reacting formaldehyde, especially paraformaldehyde, with a secondary amine in the complete or almost complete absence of a solvent. An alternative comprises reacting a diaminomethane produced from a secondary amine, formaldehyde, especially paraformaldehyde, as well as water with one another in about equimolar amounts. The invention is also concerned with a process for the aminomethylation of δ-tocopherol or of tocopherol mixtures containing this and comprises using a Mannich reagent which has been produced in the above manner. After completion of this aminomethylation process excess Mannich reagent can be separated by distillation and can be reacted with water and formaldehyde, especially paraformaldehyde, in order to regenerate further Mannich reagent suitable for use in the aminomethylation, this regeneration representing a further aspect of the invention. Finally, the invention includes certain novel bis(aminomethyl)-γ-tocopherols.
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- An efficient synthetic method for 1-N,N-dialkylamino-1,3-pentadiynes
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The diyne amines CH3C≡CC≡CNR2 (R = CH3 or C2H5) have been synthesized with greater than 50% overall yields starting from 1,4-dichloro-2-butyne, the last step being a base-catalyzed isomerization of HC≡CC≡CCH2NR2.
- Brandsma,Walda,Oosterveld
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- A quick procedure for the preparation of 1-N,N-dialkylamino-1-buten-3-ynes
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1-N,N-Dialkylamino-1-buten-3-ynes, HC≡CCH=CHNR2 (R = CH3 or C2H5, E/Z ratio ~97:3) have been prepared in 80 and 84% yields by treating the Mannich-coupling products from HC≡CCH2OCH3 and R2NCH2OH, CH3OCH2C≡CCH2NR2, with two equivalents of potassium amide in liquid ammonia and subsequently adding methanol or ammonium chloride.
- Brandsma,Verkruijsse
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p. 807 - 810
(2007/10/02)
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- Nitrite Ion as a Nitrosating Reagent. Nitrosation of Morpholine and Diethylamine in the Presence of Formaldehyde
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The kinetics of the nitrosation of morpholine and diethylamine in the presence of formaldehyde has been studied at pH values between 6.5-8.2 and 6.9-8.7, respectively.The results are interpreted through a mechanism that implies the reaction between both the nitrite NO2(-) and iminium R2N(+)=CH2 ions.The latter ion results from the dehydration of the conjugated acid of the carbinolamine, R2NH(+)CH2OH, the initial product of the amine-formaldehyde reaction.The results allow the calculation of the equlibrium constants of the formation of carbinolamine, R2NCH2OH, and methanediamine, R2NCH2NR2 (only for the morpholine-formaldehyde system), and their conjugate acids.
- Casado, Julia,Mosquera, Manuel,Paz, L. Carlos,Prieto, M. Flor Rodriguez,Tato, Jose Vazquez
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p. 1963 - 1966
(2007/10/02)
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- Preparation of esters of phosphorus acids
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Esters of phosphorus acids are prepared by an improved process whereby aromatic alcohols and phosphorus halides are reacted at specified temperatures in the presence of amine catalysts thereby providing high yields of substantially pure esters and allowing preparation of selected halogen-containing mono- and di-esters of phosphorus acids wherein halogen is directly bonded to phosphorus having substantially no side reactant contamination. The phosphorus esters are useful as intermediates in the preparation of plasticizers, oil additives and functional fluids.
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- 3-Anilino-5,5-disubstituted-2-aminomethyl-2-cyclohexen-1-ones and the salts thereof
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Novel cyclohexenone derivatives, which are shown by the general formula SPC1 Wherein each of R1 and R2 represents a hydrogen atom, lower alkyl or phenyl group; one of R3 and R4 represents a hydrogen atom or lower alkyl group, and the other represents an unsubstituted or substituted phenyl, lower alkyl or aralkyl group, or R3 and R4, taken together with the adjacent nitrogen atom, form a 5 to 6-membered heterocyclic ring; one of R5 and R6 represents a hydrogen atom or lower alkyl group, and the other represents a lower alkyl, phenyl or aralkyl group, or R5 and R6, taken together with the adjacent nitrogen atom, form an unsubstituted or substituted 5 to 6-membered heterocyclic ring, and their pharmaceutically acceptable salts, useful medicines such as analgesics.
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