CH284713A - Process for the preparation of an aromatic acylamidodiol, nitrated in the ring. - Google Patents

Process for the preparation of an aromatic acylamidodiol, nitrated in the ring.

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Publication number
CH284713A
CH284713A CH284713DA CH284713A CH 284713 A CH284713 A CH 284713A CH 284713D A CH284713D A CH 284713DA CH 284713 A CH284713 A CH 284713A
Authority
CH
Switzerland
Prior art keywords
diol
process according
fon
preparation
acylamidodiol
Prior art date
Application number
Other languages
French (fr)
Inventor
Company Parke Davis
Original Assignee
Parke Davis & Co
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 Parke Davis & Co filed Critical Parke Davis & Co
Publication of CH284713A publication Critical patent/CH284713A/en

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C237/00—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by amino groups
    • C07C237/24—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by amino groups having the carbon atom of at least one of the carboxamide groups bound to a carbon atom of a ring other than a six-membered aromatic ring of the carbon skeleton
    • C07C237/26—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by amino groups having the carbon atom of at least one of the carboxamide groups bound to a carbon atom of a ring other than a six-membered aromatic ring of the carbon skeleton of a ring being part of a condensed ring system formed by at least four rings, e.g. tetracycline

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Saccharide Compounds (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Medicines Containing Antibodies Or Antigens For Use As Internal Diagnostic Agents (AREA)

Description

Procede de preparation d'un acylamidodiol aromatique, nitre dans 1e noyau. Process for the preparation of an aromatic acylamidodiol, nitre in the nucleus.

Dans 1e brevet principal, an a decrit un proced6 de preparation du 'P-1-p-nitroph6ny 1 2-dichloroac@tamidopropane-1,3-diol. Le pr6 sent brevet a pour objet un proced6 de pr6 paration dun autre acylamidodiol aromati que, nitre dann 1e noyatt. Ce proc6de est ca racteris6 en ce que Fon Fait reagir 1e i1'-1-p nitrophenyl-2-aminopropane-1,3-diol avee un derive de 1'acide difluoroacetique, contenant au moins ttn radical F2CH-CO-, daus des conditions telles que, par fixation d'un radi cal F.CH-CO- sur 1e groupe amino, il se forme 1e 1I-1-p-nitroph@nyl-2-difluoroac@t amidopropane-1,3-diol. Ce dernier est une nouvelle substance cristallis6e. In the main patent, an described a process for the preparation of 'P-1-p-nitroph6ny 12-dichloroac@tamidopropane-1,3-diol. The subject of the present patent is a process for the preparation of another aromatic acylamidodiol, nitrate in the core. This process is characterized in that it reacts 1'-1-p nitrophenyl-2-aminopropane-1,3-diol with a difluoroacetic acid derivative, containing at least one F2CH-CO- radical, in conditions such that, by attaching a radical F.CH-CO- to the amino group, 1H-1-p-nitroph@nyl-2-difluoroac@t amidopropane-1,3-diol is formed. The latter is a new crystallized substance.

0n peut citer comme d6rives appropries pour effectuer ladite reaction de difluoro acetylation, les Halogenures, les alcoyl-esters ou 1'anliyclride de Faeide difluoroaegtiqtie.Lors qti'on eniploie tin ester dudit aride, la reac tion est effeetuee, dans des conditions anhydres. 1.joi;squ'on utilise hin halogenare ou 1'anhydride de Faeide difltioroae6tique, la reaetion peut ehre effectuee sofft dans des eonditions anhy dres, sofft en presence d'eau, et en presence ou non dune substance alcaline. Si an utilise 1'anhydride de Faeide difliioroac6tique, il est toutefois pref6rable de ne pas effeetuer la reaetion dann des conditions anhydres, dann 1e eas oiz an titilise un catalyseur alcalin. 0n can be cited as derivatives suitable for carrying out said difluoro acetylation reaction, halides, alkyl esters or anliyclride of Faeide difluoroaegtiqtie. 1.joi; squ'on uses hin halogenare or 1'anhydride difltioroae6tique Faeide, the reaction can ehre carried out sofft in anhy dres eonditions, sofft in the presence of water, and in the presence or not of an alkaline substance. If difliiroacetic acid anhydride is used, however, it is preferable not to carry out the reaction under anhydrous conditions, in case an alkaline catalyst is used.

De preference, an soumet ä ladite difluoro ae6t.ylation la forme rae6mique (dl) ou 1'iso- Preferably, an subjects to said difluoro ae6t.ylation the raemic form (dl) or the iso-

mere optiquenient actif lev ogy re du P-1-p-ni troph@nyl-2-aminopropane-1,3-diol. Le pro duit obtenu par 1e proced6 du present brevet, surtout la forme racemique et 1a. forme Ievo gyre, possede une valeur th6rapeutique comme e_.ntibiotique et se preie pour la preparation d'atttres compos6s ayant une activit6 anti biotiqtie. optically active mother lev ogy re of P-1-p-ni troph@nyl-2-aminopropane-1,3-diol. The product obtained by the process of this patent, especially the racemic form and 1a. forms a levo gyre, has therapeutic value as an antibiotic, and is useful for the preparation of compounds with antibiotic activity.

<I>Exemple 1:</I> 0n chatiffe ä reflux sur un bain ä vapeur pendant 45 minutes hin inglange compos6 de 1 @@ de dl-P-1-p-nitroph@nyl-2-aminopropane 1,3-cliol, de 3 ein, de difluoroac6ta,te d'6thy1e et de 10 6m3 d'ethanol absolu. 0n 6vapore 1'ethanol et an dissout 1e residu dann 200 cm' d'acetate d'etliyle. 0n lave l'extrait d'acetate d'6thy1e avec de Faeide sul.furique 0,1 n, puis a.v ec une solution ä. 5 1/o de bicarbonate de solide et finalement avee de 1'eau. Apres avoir seche 1a. solution, oii elimine 1'acetate d'ethyle par distillation et oii purifie 1e dl-VI-1-p-nitro phenyl-2-difluoroacetamidopropane -1,3 - diol Brut par reeristallisation dans de 1'eati. Le produit eristallise ä. partir de 1'eau sous forme d'un monohydrate, qiti eomtnence ä fondre rt 65 C. Le compos6 non hydrate repond ä la formule <I>Example 1:</I> 0n chaff at reflux on a steam bath for 45 minutes a mixture composed of 1 @@ of dl-P-1-p-nitroph@nyl-2-aminopropane 1,3-cliol , 3 ein, difluoroacetate, ethyl et 10 6m3 of absolute ethanol. The ethanol is evaporated and the residue is dissolved in 200 cm3 of ethyl acetate. The ethyl acetate extract is washed with 0.1 n sulfuric acid, then with a solution. 5 1/o baking soda and finally with water. After drying 1a. solution, where the ethyl acetate is removed by distillation and where the crude dl-VI-1-p-nitro phenyl-2-difluoroacetamidopropane-1,3-diol is purified by receristallization in eati. The product eristallizes ä. from water in the form of a monohydrate, which begins to melt at 65° C. The unhydrated compound has the formula

(forme de dl-cJ) (form of dl-cJ)

<I>Exemple 2:</I> 0n ehauffe ä reflux sur un bain ä vapeur pendant une heure, un inelange conipose de 1 g de (1)-!tf-l-p-nit-rophenv1-?-aminopropane 1,3-diol, de 3 eni-, de clifluoroaeetate d'ethyle et de 10 eine d'ethanol absolu. Dans la suite, an procede eonime deerit dann 1'exemple 1, mais an purifie 1e @l)-i1@-1-p-nitrophenyl-`' clifluoroa.cetaniiclopropane-l.,3-diol Brut, obteim par reeristallisation dann du diehlorure d'ethy lene (au lieu de 1'ea ct ; point de I!iision 94 ä 95 C; (",)D dazis Talcool : + 24" (i. <I>Example 2:</I> After heating at reflux on a steam bath for one hour, a mixture consisting of 1 g of (1)-!tf-1-p-nit-rophenyl-?-aminopropane 1,3- diol, 3 eni-, ethyl clifluoroaeetate and 10 eine of absolute ethanol. In the following, the same process as described in Example 1, but purifies the crude @1)-11@-1-p-nitrophenyl-''clifluoroa.cetaniiclopropane-1.,3-diol, obtained by receristallization in ethyl dichloride (instead of ea ct; breaking point 94 at 95 C; (")D dazis Alcohol: + 24" (i.

Claims (6)

HEVENDICATION: Procede de preparation d'iin acylamidodiol aromatique, nitre dans 1e noyau, caraeterise en ce que Fon fait reagir 1e !lI-1-p-nitrophenyl ')-aminopropane-1,3-diol. avec uxi derive de 1'acide difluoroaeetiqtie, contenant au moins un radical F"CH-CO-, dass des condi tions telles que, par fixation d'un radieal. F.CH-CO- sur 1e groupe amino, il se forme 1e '1'-l-p-nitroph6nyl-2-difluoroacetamido propane-1,3-diol. Ce eompose est une subs tance eristallisee. Le moiiohydrate de la forme racemique Fond ä environ 65 C; ]es isomeres CLAIM: Process for the preparation of an aromatic acylamidodiol, nitre in the nucleus, characterized in that Fon reacts with 1H-1-p-nitrophenyl ')-aminopropane-1,3-diol. with uxi derivative of difluoroacetic acid, containing at least one F"CH-CO- radical, under conditions such that, by attachment of a radical. F.CH-CO- to the amino group, the 1e '1'-1-p-nitrophenyl-2-difluoroacetamidopropane-1,3-diol This compound is a crystallized substance The moiiohydrate of the racemic form Melts at about 65 C; optiquement actifs (1 et d) fondent ä 94 ä 95 C; (a) D pOT1r 1.'isomere levogyre dans Talcool est de +2406. SOUS-REVENDIC ATIONS: 1. Procede sel.on ia revendication, caraete ris6 en ce que 1'on fait reagir la forme ra.ce inique (dl) du ![!-1-p-iiit.roplienyl-?-amino propane-1,3-diol. ?. Procede selon la revendication, caracte ris6 en ce que Fon fa.it reagir ]'isoniere opti que levogy re (1) du 1--1-p-nit.ropheiiyl-? aininopropane-1,3-diol. optically active (1 and d) melt at 94-95°C; (a) D pOT1r 1. levorotatory isomer in alcohol is +2406. SUB-CLAIMS: 1. Process according to claim, characterized in that the inic (dl) ra.ce form of ![!-1-p-iiit.roplienyl-?-amino propane is reacted -1,3-diol. ?. Process according to claim, character ris6 in that Fon fa.it react]'isoniere opti that levogy re (1) of 1--1-p-nit.ropheiiyl-? aininopropane-1,3-diol. 3. Procede sel.on la revendieation, earacte ris6 en ee que Fon effeetue la reaction avec un Halogenure de l.'aeide difluoroacetique. 3. Process according to the claim, the fact is that the reaction is carried out with a halide of the difluoroacetic aeide. 4. Proeede selon la revendication, caraete ris6 en ee que Von effeeiue la reaction avec un aleoyl-eater de 1'aeide difl.uoroacetique. .4. Proeede according to claim, caraete ris6 in ee that Von effeeiue the reaction with an aleoyl-eater of difl.uoroacetic 1'aeide. . 5. Proeecle selon la revendieation, earaete risA en ee que Fon effcctne la r6a(-tion avee 1'anhydride de 1'aeide clilliioroaeetique. 5. Proeecle according to the claim, earaete risA in ee that Fon effcctne the r6a (-tion avee 1'anhydride 1'aide clilliioroaeetique. 6. Procede selon la revendication et la sous-revendieation 4, eai aeterise en ee que 1'on effeettie la i-eaetion dans des eondiiions anhy dres.6. Process according to claim and sub-claim 4, and is neutralized in that the i-eaetion is carried out in anhydrous eondiiions.
CH284713D 1948-03-16 1948-12-15 Process for the preparation of an aromatic acylamidodiol, nitrated in the ring. CH284713A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US284713XA 1948-03-16 1948-03-16
CH278776T 1948-12-15

Publications (1)

Publication Number Publication Date
CH284713A true CH284713A (en) 1952-07-31

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CH284713D CH284713A (en) 1948-03-16 1948-12-15 Process for the preparation of an aromatic acylamidodiol, nitrated in the ring.

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