BE527500A - - Google Patents
Info
- Publication number
- BE527500A BE527500A BE527500DA BE527500A BE 527500 A BE527500 A BE 527500A BE 527500D A BE527500D A BE 527500DA BE 527500 A BE527500 A BE 527500A
- Authority
- BE
- Belgium
- Prior art keywords
- amides
- halogenated
- halopivalic
- preparation
- pivalic acid
- Prior art date
Links
- FYSNRJHAOHDILO-UHFFFAOYSA-N Thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 claims description 6
- 150000001408 amides Chemical class 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 4
- XSBZRCYZDXMLPH-UHFFFAOYSA-N 2,2-dimethyl-N-phenylmethoxypropanamide Chemical compound CC(C)(C)C(=O)NOCC1=CC=CC=C1 XSBZRCYZDXMLPH-UHFFFAOYSA-N 0.000 claims description 3
- HFRXJVQOXRXOPP-UHFFFAOYSA-N Thionyl bromide Chemical compound BrS(Br)=O HFRXJVQOXRXOPP-UHFFFAOYSA-N 0.000 claims description 2
- 150000003939 benzylamines Chemical class 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- 150000004820 halides Chemical class 0.000 claims description 2
- 125000005843 halogen group Chemical group 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- 238000002560 therapeutic procedure Methods 0.000 claims description 2
- 125000005546 pivalic acid group Chemical class 0.000 claims 2
- 125000004429 atoms Chemical group 0.000 claims 1
- 229910052801 chlorine Inorganic materials 0.000 claims 1
- 239000000460 chlorine Substances 0.000 claims 1
- 125000001309 chloro group Chemical group Cl* 0.000 claims 1
- VZGDMQKNWNREIO-UHFFFAOYSA-N Carbon tetrachloride Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- STOLHXQYRURNAZ-UHFFFAOYSA-N C(C1=CC=CC=C1)NC(C(CBr)(C)C)=O Chemical compound C(C1=CC=CC=C1)NC(C(CBr)(C)C)=O STOLHXQYRURNAZ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N HCl Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L na2so4 Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- AOJFQRQNPXYVLM-UHFFFAOYSA-N pyridin-1-ium;chloride Chemical compound [Cl-].C1=CC=[NH+]C=C1 AOJFQRQNPXYVLM-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- WGQKYBSKWIADBV-UHFFFAOYSA-N Benzylamine Chemical compound NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 description 1
- KGRNLUHSVAKWTK-UHFFFAOYSA-N N-benzyl-3-chloro-2,2-dimethylpropanamide Chemical compound ClCC(C)(C)C(=O)NCC1=CC=CC=C1 KGRNLUHSVAKWTK-UHFFFAOYSA-N 0.000 description 1
- UIIMBOGNXHQVGW-UHFFFAOYSA-M NaHCO3 Chemical class [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000001773 anti-convulsant Effects 0.000 description 1
- 239000001961 anticonvulsive agent Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N chlorine atom Chemical group [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C233/00—Carboxylic acid amides
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
<Desc/Clms Page number 1>
NOUVELLES AMIDES HALOGENEES ET LEURS PROCEDES DE PREPARATION.
La présente invention, à la réalisation de laquelle ont participé MM. Paul GAILLIOT et Jean ROBERT; concerne de nouvelles amides halogénées et leurs procédés de préparation. Ces nouveaux produits sont des amides d'acides halogénopivaliques de formule générale :
EMI1.1
Dans cette formule, X représente un atome de chlore ou de brome.
Ces corps peuvent être préparés, selon 1-'invention, par les méthodes connues de préparation d'amides telles que, par exemple : - Action d'un halogénure d'acide halogénopivalique
EMI1.2
ou d'un ester halogénopivalique
EMI1.3
<Desc/Clms Page number 2>
- Chauffage du sel de benzylamine d'un acide halogénopivalique.
On peut également les obtenir à partir de la N-benzyloxy-pivalamide
EMI2.1
par les méthodes connues pour remplacer un hydroxyle par un atome d'halogène (par exemple, action du chlorure ou du bromure de thionyle).
Ces produits se sont révélés des anticonvulsivants particulièrement intéressants et sont, de ce fait, utilisables en thérapeutique humaine ou vétérinaire.
Les exemples suivants, à titre non limitatif, montrent comment l'invention peut être mise en pratique.
EXEMPLE 1.
Dans une solution refroidie à 0 , de 21,45 g de benzyl-amine dans 100 cm3 d'eau,on introduit goutte à goutte en maintenant la température entre -2 et 0 et en agitant, 20 g de chlorure de oromopivalyle.
Après la fin de l'addition (1/4 d'heure), on maintient entre 0 et 10 en agitant pendant 3 heures. On filtre la N-benzylbromopivalamide qui s'est formée, lave à l'eau et sèche sous vide sulfurique. On obtient ainsi 25,3 g de produit brut qui, après recristallisation dans le cyclohexane, donnent 20,3 g de N-benzylbromopivalamide pure fondant à 52-53 .
EXEMPLE 2.
Dans une suspension, maintenue entre 0 et 10 , de 120 g de N- benzyloxypivalamide [préparée par exemple selon L. MARCILLY Bull. Soc.
Chim. (3), 31, 124 (1904)] dans 400 cm3 de tétrachlorure de carbone et 45,8 g de pyridine anhydre, on coule peu à peu, en 40 minutes, en agitant, 69,lg de chlorure de thionyle. On agite pendant une heure à la température Qrdinaire, puis porte progressivement à reflux. Après la fin du dégagement d'anhydride sulfureux (1 h 1/2), on maintient encore à l'ébullition pendant 1 heure. On refroidit, extrait avec 500 cm3 d'eau pour enlever le chlorhydrate de pyridine, épuise cette couche aqueuse avec 100 cm3 de tétrachlorure de carbone. On rassemble les extraits organiques et les lave successivement avec 250 cm3 d'acide chlorhydrique normal, 250 cm3 de bicarbonate de sodium saturé puis 250 cm3 d'eau.
On sèche sur sulfate de sodium, chasse le tétrachlorure de carbone sous vide, puis rectifie. On obtient 91 g de N-benzylchloro-pivalamide qui bout à 165-170 sous 0,5 mm.
Après recristallisation dans un mélange éther-éther de pétrole, elle fond à 49-50 '.
<Desc / Clms Page number 1>
NEW HALOGENOUS AMIDES AND THEIR PREPARATION METHODS.
The present invention, in the realization of which participated MM. Paul GAILLIOT and Jean ROBERT; relates to novel halogenated amides and processes for their preparation. These new products are amides of halopivalic acids of general formula:
EMI1.1
In this formula, X represents a chlorine or bromine atom.
These bodies can be prepared, according to 1-'invention, by known methods of preparing amides such as, for example: - Action of a halide of halopivalic acid
EMI1.2
or a halopivalic ester
EMI1.3
<Desc / Clms Page number 2>
- Heating of the benzylamine salt of a halopivalic acid.
They can also be obtained from N-benzyloxy-pivalamide
EMI2.1
by the known methods for replacing a hydroxyl with a halogen atom (for example, action of thionyl chloride or bromide).
These products have proved to be particularly advantageous anticonvulsants and are therefore usable in human or veterinary therapy.
The following examples, without limitation, show how the invention can be put into practice.
EXAMPLE 1.
In a solution cooled to 0, of 21.45 g of benzyl-amine in 100 cm3 of water, is introduced dropwise while maintaining the temperature between -2 and 0 and with stirring, 20 g of oromopivalyl chloride.
After the end of the addition (1/4 hour), the mixture is maintained between 0 and 10 with stirring for 3 hours. The N-benzylbromopivalamide which has formed is filtered off, washed with water and dried under sulfuric vacuum. 25.3 g of crude product are thus obtained which, after recrystallization from cyclohexane, give 20.3 g of pure N-benzylbromopivalamide, melting point 52-53.
EXAMPLE 2.
In a suspension, maintained between 0 and 10, of 120 g of N-benzyloxypivalamide [prepared for example according to L. MARCILLY Bull. Soc.
Chim. (3), 31, 124 (1904)] in 400 cm3 of carbon tetrachloride and 45.8 g of anhydrous pyridine, is gradually poured over 40 minutes, with stirring, 69.1g of thionyl chloride. Stirred for one hour at Qrdinary temperature, then gradually brought to reflux. After the end of the evolution of sulfur dioxide (1 1/2 hours), the mixture is still boiling for 1 hour. Cooled, extracted with 500 cm3 of water to remove the pyridine hydrochloride, this aqueous layer is exhausted with 100 cm3 of carbon tetrachloride. The organic extracts are combined and washed successively with 250 cm3 of normal hydrochloric acid, 250 cm3 of saturated sodium bicarbonate and then 250 cm3 of water.
Dried over sodium sulphate, the carbon tetrachloride is driven off under vacuum, then rectified. 91 g of N-benzylchloro-pivalamide are obtained, which boils at 165-170 under 0.5 mm.
After recrystallization from an ether-petroleum ether mixture, it melts at 49-50 °.
Claims (1)
Publications (1)
Publication Number | Publication Date |
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BE527500A true BE527500A (en) |
Family
ID=161120
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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BE527500D BE527500A (en) |
Country Status (1)
Country | Link |
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BE (1) | BE527500A (en) |
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0
- BE BE527500D patent/BE527500A/fr unknown
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