CH414670A - Process for preparing O-substituted hydroxylamines - Google Patents

Process for preparing O-substituted hydroxylamines

Info

Publication number
CH414670A
CH414670A CH1252863A CH1252863A CH414670A CH 414670 A CH414670 A CH 414670A CH 1252863 A CH1252863 A CH 1252863A CH 1252863 A CH1252863 A CH 1252863A CH 414670 A CH414670 A CH 414670A
Authority
CH
Switzerland
Prior art keywords
hydroxylamines
substituted
preparing
formula
substituted hydroxylamines
Prior art date
Application number
CH1252863A
Other languages
French (fr)
Inventor
Nicolaus Bruno J R
Testa Emilio
Original Assignee
Lepetit Spa
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Lepetit Spa filed Critical Lepetit Spa
Publication of CH414670A publication Critical patent/CH414670A/en

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
    • C07D209/44—Iso-indoles; Hydrogenated iso-indoles
    • C07D209/48—Iso-indoles; Hydrogenated iso-indoles with oxygen atoms in positions 1 and 3, e.g. phthalimide

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Description

  

  
 



  Procédé de préparation d'hydroxylamines   O substituées   
 La présente invention a pour objet un procédé de préparation de O-alcoyl-hydroxylamines et de Oaralcoyl-hydroxylamines.



   On sait que l'alcoylation directe des hydroxylamines conduit généralement aux dérivés N-alcoylés.



  Pour obtenir des hydroxylamines O-alcoylées, il est donc nécessaire de protéger le groupe amino de l'hydroxylamine. Le dérivé O-alcoylé est ensuite soumis à un traitement destiné à scinder le groupe protégeant le groupe amino sans affecter simultanément le groupe O-alcoyle.   I1    en résulte que les rendements sont généralement bas.



   Le procédé selon l'invention, pour la préparation d'hydroxylamines O-substituées de formule    R-O-NH2    dans laquelle R représente un groupe alcoyle ou aralcoyle à chaîne droite ou ramifiée, est caractérisé en ce que   l'on    fait bouillir à reflux un phtalimide de formule
EMI1.1     
 avec un hydrate d'hydrazine dans un alcool aliphatique inférieur. Après refroidissement, on sépare en règle générale le précipité par filtration et on peut évaporer le filtrat à sec sous vide. Le résidu est l'hydroxylamine O-substituée désirée sous forme de chlorhydrate, dont on peut isoler la base libre de manière connue.



   Le schéma de la réaction est le suivant:
EMI1.2     

 R représentant un groupe alcoyle ou aralcoyle.



   Exemple I
 Chlorhydrate de O-éthyl-hydroxylamine
 On ajoute 1,45 g d'hydrate d'hydrazine à 98   o/o    à une solution de 5,4 g de N-éthoxy-phtalimide dans 25   ml    d'éthanol et on fait bouillir le mélange à reflux pendant 5 min. Après addition de 3,5   ml    d'acide chlorhydrique concentré, on continue à chauffer à reflux pendant encore 5 min. Après avoir refroidi le mélange réactionnel et l'avoir dilué avec 10   ml    d'eau, on filtre pour séparer le précipité, formé de phtalhydrazide, et on évapore le filtrat à sec sous vide.



  On recristallise le résidu dans un mélange d'éthanol et d'éther éthylique. On obtient finalement 2,4 g (85   O/o)    de chlorhydrate de O-éthyl-hydroxylamine, p.f. 125-1270 C.  
  



  
 



  Process for preparing O-substituted hydroxylamines
 The present invention relates to a process for the preparation of O-alkyl-hydroxylamines and of Oaralkyl-hydroxylamines.



   It is known that the direct alkylation of hydroxylamines generally leads to N-alkylated derivatives.



  In order to obtain O-alkylated hydroxylamines, it is therefore necessary to protect the amino group of the hydroxylamine. The O-alkyl derivative is then subjected to a treatment intended to cleave the group protecting the amino group without simultaneously affecting the O-alkyl group. As a result, the yields are generally low.



   The process according to the invention, for the preparation of O-substituted hydroxylamines of formula RO-NH2 in which R represents an alkyl or aralkyl group having a straight or branched chain, is characterized in that a phthalimide is boiled under reflux. formula
EMI1.1
 with a hydrazine hydrate in a lower aliphatic alcohol. After cooling, the precipitate is generally filtered off and the filtrate can be evaporated to dryness in vacuo. The residue is the desired O-substituted hydroxylamine in hydrochloride form, from which the free base can be isolated in known manner.



   The reaction scheme is as follows:
EMI1.2

 R representing an alkyl or aralkyl group.



   Example I
 O-ethyl-hydroxylamine hydrochloride
 1.45 g of 98% hydrazine hydrate is added to a solution of 5.4 g of N-ethoxy-phthalimide in 25 ml of ethanol and the mixture is boiled under reflux for 5 min. After addition of 3.5 ml of concentrated hydrochloric acid, heating is continued under reflux for a further 5 min. After cooling the reaction mixture and diluting it with 10 ml of water, it is filtered to separate the precipitate, formed from phthalhydrazide, and the filtrate is evaporated to dryness in vacuo.



  The residue is recrystallized from a mixture of ethanol and ethyl ether. Finally obtained 2.4 g (85 O / o) of O-ethyl-hydroxylamine hydrochloride, m.p. 125-1270 C.

Claims (1)

Exemples 2 à 4 En procédant de manière semblable, on a préparé les chlorhydrates d'hydroxylamines O-substituées suivantes: Isopropyle p.f. 75- 760C rendement 78 0/o Butyle p.f. 148-1500C rendement 74 8/o Benzyle sup. à 2300C rendement 80 o/o (sublimation) REVENDICATION Procédé de préparation d'hydroxylamines O-substituées de formule R-O-NH2 dans laquelle R représente un groupe alcoyle ou aralcoyle à chaîne droite ou ramifiée, caractérisé en ce que l'on fait bouillir à reflux un phtalimide de formule EMI2.1 avec un hydrate d'hydrazine dans un alcool aliphatique inférieur. Examples 2 to 4 By proceeding in a similar manner, the following O-substituted hydroxylamine hydrochlorides were prepared: Isopropyl m.p. 75- 760C yield 78 0 / o Butyl m.p. 148-1500C efficiency 74 8 / o Benzyl sup. at 2300C efficiency 80 o / o (sublimation) CLAIM Process for the preparation of O-substituted hydroxylamines of formula R-O-NH2 in which R represents a straight or branched chain alkyl or aralkyl group, characterized in that a phthalimide of formula is boiled under reflux. EMI2.1 with a hydrazine hydrate in a lower aliphatic alcohol.
CH1252863A 1962-10-12 1963-10-11 Process for preparing O-substituted hydroxylamines CH414670A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
GB3875862A GB986213A (en) 1962-10-12 1962-10-12 Process for preparing hydroxylamines

Publications (1)

Publication Number Publication Date
CH414670A true CH414670A (en) 1966-06-15

Family

ID=10405517

Family Applications (1)

Application Number Title Priority Date Filing Date
CH1252863A CH414670A (en) 1962-10-12 1963-10-11 Process for preparing O-substituted hydroxylamines

Country Status (2)

Country Link
CH (1) CH414670A (en)
GB (1) GB986213A (en)

Also Published As

Publication number Publication date
GB986213A (en) 1965-03-17

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