BE506694A - - Google Patents
Info
- Publication number
- BE506694A BE506694A BE506694DA BE506694A BE 506694 A BE506694 A BE 506694A BE 506694D A BE506694D A BE 506694DA BE 506694 A BE506694 A BE 506694A
- Authority
- BE
- Belgium
- Prior art keywords
- piperazine
- carboxamide
- preparation
- dimethylene
- carbonyl
- Prior art date
Links
- VEXZGXHMUGYJMC-UHFFFAOYSA-N HCl Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 7
- 238000002360 preparation method Methods 0.000 claims description 5
- NOWKCMXCCJGMRR-UHFFFAOYSA-N aziridine Chemical compound C1CN1 NOWKCMXCCJGMRR-UHFFFAOYSA-N 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 238000000034 method Methods 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- 125000005270 trialkylamine group Chemical group 0.000 claims description 2
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 125000003917 carbamoyl group Chemical class [H]N([H])C(*)=O 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- GGOLVOARSIMXMZ-UHFFFAOYSA-N ethyl 4-carbonochloridoylpiperazine-1-carboxylate Chemical compound CCOC(=O)N1CCN(C(Cl)=O)CC1 GGOLVOARSIMXMZ-UHFFFAOYSA-N 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- FBAIGEMWTOSCRU-UHFFFAOYSA-N 4-methylpiperazine-1-carbonyl chloride Chemical compound CN1CCN(C(Cl)=O)CC1 FBAIGEMWTOSCRU-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- SLUNEGLMXGHOLY-UHFFFAOYSA-N benzene;hexane Chemical compound CCCCCC.C1=CC=CC=C1 SLUNEGLMXGHOLY-UHFFFAOYSA-N 0.000 description 1
- 230000000875 corresponding Effects 0.000 description 1
- USYYUUDWGLOMDJ-UHFFFAOYSA-N ethyl 4-methylpiperazine-1-carboxylate Chemical compound CCOC(=O)N1CCN(C)CC1 USYYUUDWGLOMDJ-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- YGYAWVDWMABLBF-UHFFFAOYSA-N phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 1
- GLUUGHFHXGJENI-UHFFFAOYSA-N piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 1
- IVXQBCUBSIPQGU-UHFFFAOYSA-N piperazine-1-carboxamide Chemical class NC(=O)N1CCNCC1 IVXQBCUBSIPQGU-UHFFFAOYSA-N 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
- C07D295/16—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms acylated on ring nitrogen atoms
- C07D295/20—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms acylated on ring nitrogen atoms by radicals derived from carbonic acid, or sulfur or nitrogen analogues thereof
- C07D295/215—Radicals derived from nitrogen analogues of carbonic acid
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D203/00—Heterocyclic compounds containing three-membered rings with one nitrogen atom as the only ring hetero atom
- C07D203/04—Heterocyclic compounds containing three-membered rings with one nitrogen atom as the only ring hetero atom not condensed with other rings
- C07D203/06—Heterocyclic compounds containing three-membered rings with one nitrogen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
- C07D203/16—Heterocyclic compounds containing three-membered rings with one nitrogen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with acylated ring nitrogen atoms
- C07D203/20—Heterocyclic compounds containing three-membered rings with one nitrogen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with acylated ring nitrogen atoms by carbonic acid, or by sulfur or nitrogen analogues thereof, e.g. carbamates
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Description
<Desc/Clms Page number 1>
,PROCEDE DE PREPARATION DE MONOC ARBOXAMIDES DE LA PIPERAZINE.
Le brevet d'invention se rapporte à la préparation de monocar- boxamides de la pipérazine correspondant à la formule : ,
EMI1.1
dans laquelle R représente un groupe alcoyle et X un dérivé de carboxamide.
Le présent perfectionnement est relatif à la préparation de nouveaux composés de ce genre, dans lesquels R désigne un groupe alcoyle ou un groupe carboxy estérifié et X un dérivé de carboxamide non décrit dans le brevet d'invention, plus particulièrement de la diméthylène-carboxamide
EMI1.2
Ces composés se préparent d'après le procédé décrit dans le brevet d'invention par réaction entre le chlorure du R-pipérazine-carbonyle, ou de son chlorhydrate, et de l'éthylène-imine. L'acide chlorhydrique formé par la réaction est fixé au moyen d'un accepteur d'acide convenable, par exemple une trialcoylamine. La réaction est effectuée en présence d'un solvant organique et à une température ne dépassant en général pas la température ambiante.
Exemple 1. - Préparation de 1-méthylpipérazine-4-NN-diméthylène-carboxamide.
On ajoute 40 g de monochlorhydrate du chlorure de 1-méthylpipé-
<Desc/Clms Page number 2>
razine-4-carbonyle à une solution de 8,6 g d'éthylène-imine et de 40,4 g de triéthylamine dans 300 cm3 de benzène. L'addition doit se faire avec agita- tion énergique de la solution et sans dépasser la température de 10 C.
On filtre le chlorhydrate de triéthylamine. On élimine le sol- vant sous pression réduite et on distille le résidu. On obtient 22,5 g de l-méthylpipérazine-4-NN-diméthylène-carboxamide. Ce produit distille à 85- 90 C sous une pression de 0,5 mm Hg. Il se polymérise lentement à la tempe- rature ambiante.
Exemple 2. Préparation de 1-carbéthoxypipérazine-4-NN- diméthylène-carboxa- mide.
On ajoute 67 g de chlorure de 1-carbéthoxy-pipérazine-4-carbonyle, dissous dans 100 cm3 de benzène, à une solution de 13 g d'éthylène-imine et 31 g de triéthylamine dissous dans 200 cm3 de benzène. On doit agiter éner- giquement et ne pas-dépasser 5 C. Après quelque temps, on filtre le chlorhy- drate de triéthylamineo On élimine le solvant sous pression réduite et on distille le résidu sous vide poussé. On obtient'57 g de 1-oarbéthoxypipéra- zine-4-NN-diméthylène-carboxamide. Ce produit cristallise lentement (P.F. après recristallisation dans un mélange benzène-hexane = 58 C). Il distille vers 137 0 sous une pression de 0,5 mm Hg.
Le chlorure de 1-carbéthoxypipérazine-4-carbonyle peut être pré- paré soit par.une méthode analogue à celle décrite dans le brevet d'invention pour le chlorure du 1-méthyl-pipérazine-4-carbonyle, soit par action du phos- gène sur la 1-méthyl-4-carbéthoxy-pipérazine. (Bull. Soc. chim. Belgique, 58, (1949), 110).
<Desc / Clms Page number 1>
, PROCESS FOR PREPARING MONOC ARBOXAMIDES OF PIPERAZINE.
The invention patent relates to the preparation of piperazine monocarboxamides corresponding to the formula:,
EMI1.1
wherein R represents an alkyl group and X a carboxamide derivative.
The present improvement relates to the preparation of new compounds of this type, in which R denotes an alkyl group or an esterified carboxy group and X a carboxamide derivative not described in the invention patent, more particularly dimethylene-carboxamide.
EMI1.2
These compounds are prepared according to the process described in the invention patent by reaction between the chloride of R-piperazine-carbonyl, or its hydrochloride, and ethylene-imine. The hydrochloric acid formed by the reaction is fixed by means of a suitable acid acceptor, for example a trialkylamine. The reaction is carried out in the presence of an organic solvent and at a temperature generally not exceeding room temperature.
Example 1. - Preparation of 1-methylpiperazine-4-NN-dimethylene-carboxamide.
40 g of 1-methylpipe-chloride monohydrochloride are added.
<Desc / Clms Page number 2>
razin-4-carbonyl to a solution of 8.6 g of ethylene imine and 40.4 g of triethylamine in 300 cm3 of benzene. The addition must be made with vigorous stirring of the solution and without exceeding the temperature of 10 C.
The triethylamine hydrochloride is filtered off. The solvent is removed under reduced pressure and the residue is distilled. 22.5 g of 1-methylpiperazine-4-NN-dimethylene-carboxamide are obtained. This product distils at 85-90 ° C under a pressure of 0.5 mm Hg. It slowly polymerizes at room temperature.
Example 2. Preparation of 1-carbethoxypiperazine-4-NN-dimethylene-carboxamide.
67 g of 1-carbethoxy-piperazine-4-carbonyl chloride, dissolved in 100 cm3 of benzene, are added to a solution of 13 g of ethyleneimine and 31 g of triethylamine dissolved in 200 cm3 of benzene. Stir vigorously and not exceed 5 ° C. After some time, the triethylamine hydrochloride is filtered off. The solvent is removed under reduced pressure and the residue is distilled off under high vacuum. 57 g of 1-arbethoxypiperazine-4-NN-dimethylene-carboxamide are obtained. This product crystallizes slowly (m.p. after recrystallization from a benzene-hexane mixture = 58 C). It distils to around 137 0 under a pressure of 0.5 mm Hg.
1-Carbethoxypiperazine-4-carbonyl chloride can be prepared either by a method analogous to that described in the invention patent for 1-methyl-piperazine-4-carbonyl chloride, or by the action of phos- gene for 1-methyl-4-carbethoxy-piperazine. (Bull. Soc. Chim. Belgium, 58, (1949), 110).
Claims (1)
Publications (1)
| Publication Number | Publication Date |
|---|---|
| BE506694A true BE506694A (en) |
Family
ID=146883
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| BE506694D BE506694A (en) |
Country Status (1)
| Country | Link |
|---|---|
| BE (1) | BE506694A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2478097A1 (en) * | 1980-02-15 | 1981-09-18 | Mitsui Toatsu Chemicals | NOVEL DERIVATIVES OF PIPERAZINE, THEIR PREPARATION AND IMMUNOLOGICAL APPLICATIONS |
-
0
- BE BE506694D patent/BE506694A/fr unknown
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2478097A1 (en) * | 1980-02-15 | 1981-09-18 | Mitsui Toatsu Chemicals | NOVEL DERIVATIVES OF PIPERAZINE, THEIR PREPARATION AND IMMUNOLOGICAL APPLICATIONS |
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