BE538254A - - Google Patents
Info
- Publication number
- BE538254A BE538254A BE538254DA BE538254A BE 538254 A BE538254 A BE 538254A BE 538254D A BE538254D A BE 538254DA BE 538254 A BE538254 A BE 538254A
- Authority
- BE
- Belgium
- Prior art keywords
- thio
- water
- heterocyclic compound
- amino acids
- formula
- Prior art date
Links
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 150000002391 heterocyclic compounds Chemical class 0.000 claims description 6
- HIVLDXAAFGCOFU-UHFFFAOYSA-N ammonium hydrosulfide Chemical compound [NH4+].[SH-] HIVLDXAAFGCOFU-UHFFFAOYSA-N 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 3
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims 1
- RWSOTUBLDIXVET-UHFFFAOYSA-M hydrosulfide Chemical compound [SH-] RWSOTUBLDIXVET-UHFFFAOYSA-M 0.000 claims 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- 125000000879 imine group Chemical group 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 2
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- VFYFMNCKPJDAPV-UHFFFAOYSA-N 2,2'-(5-oxo-1,3-dioxolan-4,4-diyl)diessigs Chemical compound C1N(C2)CN3CN1CN2C3.OC(=O)CC1(CC(O)=O)OCOC1=O VFYFMNCKPJDAPV-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- APVPOHHVBBYQAV-UHFFFAOYSA-N n-(4-aminophenyl)sulfonyloctadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NS(=O)(=O)C1=CC=C(N)C=C1 APVPOHHVBBYQAV-UHFFFAOYSA-N 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- -1 nitrogenous compound Chemical class 0.000 description 1
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
<Desc/Clms Page number 1>
Procédé pour la préparation d'acides thio-aminiques renfermant des groupements imine..
La présente invention concerne un procédé pour la préparation d'acides thio-aminiques nouveaux ayant la formule
EMI1.1
qui renferment dans la chaîne deux groupements imine séparés l'un de l'autre.
On obtient les acides thio-aminiques désirés lorsqu'on convertit un composé azoté, hétérocyclique ayant la formule
EMI1.2
<Desc/Clms Page number 2>
avec des sulfhydrures anhydres, et plus particulièrement avec le sulf)hydrure ammonique. Le composé hétérocyclique peut être facilement converti d'après le mode de réaction suivant, déjà connu :
desaldéhydes, tels que la formaldéhyde, l'acétaldéhyde ou la benzaldéhyde réagissent notamment avec le nitrile de l'acide acrylique, l'acide chlorhydrique et de la vapeur d'eau en phase gazeuse et en présence de catalyseurs, tels que par exemple le phosphate de bore, avec formation d'amides de l'acide alcoylide-, ou aralcoylide-bis-chloropropionique ayant la formule générale
EMI2.1
Si sur ce dichlorure on fait agir de l'ammoniaque liquide à la température ambiante, on obtient la monoamine correspondant à ce composé. De cette monoamine on obtient ensuite le composé azoté, hétérocyclique, mentionné ci-dessus, si on le force, notamment sous vide, à séparer quantitativement le HCl.
Le composé hétérocyclique formé réagit ensuite suivant la présente invention avec les sulfhydrures tels que par exemple le sulfhydrure ammonique, avec formation d'un acide thio-aminique, renfermant des groupements imine: dans la chaîne, Pour réaliser la réaction, la présence de petites quantités d'eau, pouvant être introduites par addition, est indispensable. On a pu notamment observer que la réaction ne peut pas être réalisée si l'on emploie pour cette réaction soit des sulfhydrures renfermant , de l'eau, soit en introduisant trop d'eau dans la réaction. Il est avantageux de ne pas employer plus de 10% environ d'eau,
<Desc/Clms Page number 3>
calculés par rapport à la quantité de composé de départ.
Les acides thio-aminiques formés conviennent comme produits de départ pour les réactions de polycondensation ou comme stabilisateurs à la chaleur pour les composés thermoplas- tiques.
Exemple 1.
10 gr. du composé hétérocyclique
EMI3.1
sont mélangés avec 10 gr. de sulfhydrure ammonique et on ajoute environ 1 cm3 d'eau à ce mélange. Déjà après quelques minutes il se produit une dissolution complète, de laquelle se séparent aussitôt des cristaux. La substance séparée par cristallisation dans/l'éthanol représente l'acide thio-aminique désiré et a un point de fusion de 177 C.
Exemple 2.
5 gr. du composé hétérocyclique
EMI3.2
sont mélangés avec environ 5 gr. de sulfhydrure ammonique solide, anhydre,et à ce mélange on ajoute environ 0,5 cm3 d'eau. Après un temps très court il se produit déjà une dissolution complète de ce mélange, duquel se séparent aussitôt des cristaux. L'acide thio-aminique formé ayant la formule
EMI3.3
est séparé par cristallisation dans l'éthanol et est obtenu directement à l'état pur.
<Desc / Clms Page number 1>
Process for the preparation of thio-amino acids containing imine groups.
The present invention relates to a process for the preparation of novel thio-amino acids having the formula
EMI1.1
which contain in the chain two imine groups separated from each other.
The desired thio-amino acids are obtained when a nitrogenous, heterocyclic compound having the formula
EMI1.2
<Desc / Clms Page number 2>
with anhydrous sulfhydrides, and more particularly with ammonium sulf) hydride. The heterocyclic compound can be easily converted according to the following reaction mode, already known:
aldehydes, such as formaldehyde, acetaldehyde or benzaldehyde react in particular with the nitrile of acrylic acid, hydrochloric acid and water vapor in the gas phase and in the presence of catalysts, such as for example phosphate of boron, with formation of amides of alkylide-, or aralkylide-bis-chloropropionic acid having the general formula
EMI2.1
If liquid ammonia is allowed to act on this dichloride at room temperature, the monoamine corresponding to this compound is obtained. From this monoamine one then obtains the nitrogenous compound, heterocyclic, mentioned above, if it is forced, in particular under vacuum, to separate the HCl quantitatively.
The heterocyclic compound formed then reacts according to the present invention with hydrosulfurides such as, for example, ammonium hydrosulfide, with the formation of a thio-amino acid, containing imine groups: in the chain, to carry out the reaction, the presence of small quantities of water, which can be introduced by addition, is essential. It has been observed in particular that the reaction cannot be carried out if one employs for this reaction either sulfhydrides containing water, or by introducing too much water into the reaction. It is advantageous not to use more than about 10% of water,
<Desc / Clms Page number 3>
calculated with respect to the amount of starting compound.
The thio-amino acids formed are suitable as starting materials for polycondensation reactions or as heat stabilizers for thermoplastic compounds.
Example 1.
10 gr. of the heterocyclic compound
EMI3.1
are mixed with 10 gr. of ammonium hydrosulphide and about 1 cm3 of water is added to this mixture. Already after a few minutes complete dissolution occurs, from which crystals immediately separate. The substance crystallized out from / ethanol represents the desired thio-amino acid and has a melting point of 177 C.
Example 2.
5 gr. of the heterocyclic compound
EMI3.2
are mixed with about 5 gr. of solid, anhydrous ammonium hydrosulphide, and to this mixture is added about 0.5 cm3 of water. After a very short time a complete dissolution of this mixture occurs, from which crystals immediately separate. The thio-amino acid formed having the formula
EMI3.3
is separated by crystallization from ethanol and is obtained directly in the pure state.
Claims (1)
Publications (1)
| Publication Number | Publication Date |
|---|---|
| BE538254A true BE538254A (en) |
Family
ID=168348
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| BE538254D BE538254A (en) |
Country Status (1)
| Country | Link |
|---|---|
| BE (1) | BE538254A (en) |
-
0
- BE BE538254D patent/BE538254A/fr unknown
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