CH302010A - Process for preparing a 4-biphenylyl-acylamidomethyl-ketone. - Google Patents
Process for preparing a 4-biphenylyl-acylamidomethyl-ketone.Info
- Publication number
- CH302010A CH302010A CH302010DA CH302010A CH 302010 A CH302010 A CH 302010A CH 302010D A CH302010D A CH 302010DA CH 302010 A CH302010 A CH 302010A
- Authority
- CH
- Switzerland
- Prior art keywords
- ketone
- biphenylyl
- reaction
- carried out
- acylamidomethyl
- Prior art date
Links
- 238000004519 manufacturing process Methods 0.000 title 1
- 238000000034 method Methods 0.000 claims description 11
- -1 4-biphenylyl-dichloroacetamidomethyl-ketone Chemical compound 0.000 claims description 6
- JXTHNDFMNIQAHM-UHFFFAOYSA-N dichloroacetic acid Chemical class OC(=O)C(Cl)Cl JXTHNDFMNIQAHM-UHFFFAOYSA-N 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 5
- 150000003839 salts Chemical class 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- FBCCMZVIWNDFMO-UHFFFAOYSA-N dichloroacetyl chloride Chemical compound ClC(Cl)C(Cl)=O FBCCMZVIWNDFMO-UHFFFAOYSA-N 0.000 claims description 4
- RQHMQURGSQBBJY-UHFFFAOYSA-N (2,2-dichloroacetyl) 2,2-dichloroacetate Chemical compound ClC(Cl)C(=O)OC(=O)C(Cl)Cl RQHMQURGSQBBJY-UHFFFAOYSA-N 0.000 claims description 3
- RSBQFKJVGZVGFM-UHFFFAOYSA-N 1,3-diaminopropan-2-one Chemical compound NCC(=O)CN RSBQFKJVGZVGFM-UHFFFAOYSA-N 0.000 claims description 2
- 238000002844 melting Methods 0.000 claims description 2
- 230000008018 melting Effects 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims 1
- 239000011541 reaction mixture Substances 0.000 description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- YATARFQKDMWTKM-UHFFFAOYSA-N C1(=CC=C(C=C1)C(N)C(=O)C(C1=CC=C(C=C1)C1=CC=CC=C1)N)C1=CC=CC=C1 Chemical compound C1(=CC=C(C=C1)C(N)C(=O)C(C1=CC=C(C=C1)C1=CC=CC=C1)N)C1=CC=CC=C1 YATARFQKDMWTKM-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- PASDCCFISLVPSO-UHFFFAOYSA-N benzoyl chloride Chemical compound ClC(=O)C1=CC=CC=C1 PASDCCFISLVPSO-UHFFFAOYSA-N 0.000 description 2
- 229960005215 dichloroacetic acid Drugs 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical class OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- YNTJVVSACQIZRZ-UHFFFAOYSA-N CC(NC(C(C(C(C=C1)=CC=C1C1=CC=CC=C1)NC(C)=O)=O)C(C=C1)=CC=C1C1=CC=CC=C1)=O Chemical compound CC(NC(C(C(C(C=C1)=CC=C1C1=CC=CC=C1)NC(C)=O)=O)C(C=C1)=CC=C1C1=CC=CC=C1)=O YNTJVVSACQIZRZ-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- 239000003513 alkali Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 235000010216 calcium carbonate Nutrition 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 235000014380 magnesium carbonate Nutrition 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000011736 potassium bicarbonate Substances 0.000 description 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- 235000015497 potassium bicarbonate Nutrition 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 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
Procédé de préparation d'une 4-biphénylyl-aeylamidométhyl-cétone. Dans le brevet principal, on a décrit un procédé de préparation de la 4-biphénylyl- acétamidométhyl-cétone.
Le présent brevet a pour objet un procédé clé préparation d'une autre 4-biphénylyl-aeyl- amidométhyl-cétone, c'est-à-dire de la 4-bi- phénylyl-dichloracétamidométhyl-cétone. Ce procédé est caractérisé en ce que l'on fait réagir un sel de la 4-biphénylyl-aminométhyl- cétone de formule
EMI0001.0010
avec un dérivé de l'acide dichloracétique con tenant an moins un groupe C1@CFICO-. La.
4-biphénylyl - dichloracétamidométhyl - cétone ainsi obtenue est une nouvelle substance cristallisée qui fond à 175-176 C et sert de produit intermédiaire pour la préparation de composés à activité antibiotique.
Comme agent. de dichloracétylation, on peut utiliser l'anhydride dichloracétique ou le chlorure de dichloracétyle. Lorsque l'on utilise le chlorure de dichloracétyle, on effec tue la, réaction dans des conditions anhydres, mais lorsqu'on utilise l'anhydride dichloracé- tique, on peut effectuer la réaction dans des conditions soit aqueuses, soit anhydres.
De préférence, on effectue le procédé selon l'invention dans un milieu faiblement alcalin. De telles conditions peuvent être réalisées soit par adjonction d'une substance faiblement alcaline au mélange réactionnel, soit par em ploi d'un solvant faiblement alcalin, tel que la diméthylformamide. Parmi les substances faiblement alcalines pouvant être ajoutées au mélange réactionnel, on peut citer les sels de métaux alcalins d'acides organiques, les car bonates et bicarbonates alcalins ou alcalino- terreux, les amines organiques tertiaires, les hydroxydes de métaux amphotères, l'hydroxyde de calcium et analogues.
Quelques exemples spécifiques de telles substances sont l'acétate de sodium, le bicar bonate de sodium, le bicarbonate de potas sium, le carbonate de sodium, le carbonate de calcium, le carbonate de magnésium, la pyridine, la quinoléine, la triéthylamine et l'hydroxyde d'aluminium.
La température utilisée pour exécuter le procédé selon l'invention peut varier dans des assez grandes limites. D'ordinaire, on utilise des températures allant de 0 C à 130 C; toutefois, quand on utilise un mélange réac tionnel aqueux, il est préférable de maintenir la température dans le voisinage de la tempé rature ordinaire ou au-dessous de celle-ci. Comme produit de départ, on peut em ployer n'importe quel sel de la 4-biphénylyl- aminométhyl-cétone. Ces sels peuvent. être obtenus en deux étapes, comme décrit dans le brevet principal.
L'invention est illustrée plus en détail par les exemples suivants: Exemple <I>I:</I> On ajoute 356 g de chlorure de diehlor- acéty le à une suspension de 463 g du chlor hydrate de la -1-biphénylyl-aminométhyl-cétone dans 1620 cm3 de diméthyl-formamide, et. on brasse le mélange mécaniquement pendant en viron 3 heures. Au début de la réaction, la température s'élève à environ 60 C. Après 3 heures de réaction, on verse le mélange réactionnel, en brassant, dans 8,33 litres d'eau et on brasse encore pendant 1 heure.
On recueille le produit solide, on le lave avec de l'eau et ensuite à l'aide d'éther de pétrole. Si on le désire, on peut purifier la. .1-biphé- nylyl-dieMoracétamidom6thy-1-cétone ainsi ob tenue par recristallisation dans de l'acétate d'éthyle; point. de fusion:175-176 C.
Ce pro duit répond à la formule
EMI0002.0014
Exeînple <I>II:</I> Un mélange formé de 52 g d'acide di- chloracétique et de 56,
5 g de chlorure de benzoyle est ajouté à 50 g de chlorhydrate de 4-biphénylyl-aminométhyl-cétone dans 250 cm-' de chlorbenzène. On chauffe le mélange réac tionnel à 85 C pour amorcer la réaction et pour accélérer la formation du chlorure de dichloracétyle par interaction de l'acide di- ehloracétique et du chlorure de benzoyle. On maintient la température du mélange réac tionnel pendant une heure à 85 C et on élève ensuite la température à l25 C pendant une demi-heure.
Puis on filtre le mélange réactionnel à. l'état chaud et on laisse refroi dir le filtrat. On recueille la 4-biphénylyl-cli- ehloracétamidométhyl-cétone insoluble et on la purifie par recristallisation dans de l'acé tate d'éthyle; point de fusion: 1.75-176 C.
Process for the preparation of a 4-biphenylyl-aeylamidomethyl-ketone. In the main patent, a process for the preparation of 4-biphenylyl-acetamidomethyl-ketone has been described.
The present patent relates to a key process for the preparation of another 4-biphenylyl-aeyl-amidomethyl-ketone, i.e. 4-bi-phenylyl-dichloroacetamidomethyl-ketone. This process is characterized in that a salt of 4-biphenylyl-aminomethyl-ketone of formula
EMI0001.0010
with a dichloroacetic acid derivative containing at least one C1 @ CFICO- group. The.
4-biphenylyl - dichloroacetamidomethyl - ketone thus obtained is a new crystalline substance which melts at 175-176 C and serves as an intermediate for the preparation of compounds with antibiotic activity.
As agent. for dichloroacetylation, dichloroacetic anhydride or dichloroacetyl chloride can be used. When dichloroacetyl chloride is used, the reaction is carried out under anhydrous conditions, but when dichloroacetic anhydride is used, the reaction can be carried out under either aqueous or anhydrous conditions.
Preferably, the process according to the invention is carried out in a weakly alkaline medium. Such conditions can be achieved either by adding a weakly alkaline substance to the reaction mixture, or by using a weakly alkaline solvent, such as dimethylformamide. Among the weakly alkaline substances which may be added to the reaction mixture, mention may be made of alkali metal salts of organic acids, alkali or alkaline earth carbonates and bicarbonates, tertiary organic amines, amphoteric metal hydroxides, hydroxide. calcium and the like.
Some specific examples of such substances are sodium acetate, sodium bicarbonate, potassium bicarbonate, sodium carbonate, calcium carbonate, magnesium carbonate, pyridine, quinoline, triethylamine and l. aluminum hydroxide.
The temperature used to carry out the process according to the invention can vary within fairly large limits. Usually, temperatures ranging from 0 C to 130 C are used; however, when using an aqueous reaction mixture, it is preferable to maintain the temperature in the vicinity of or below room temperature. As the starting material, any salt of 4-biphenylyl-aminomethyl-ketone can be employed. These salts can. be obtained in two stages, as described in the main patent.
The invention is illustrated in more detail by the following examples: Example <I> I: </I> 356 g of diehloracetyl chloride are added to a suspension of 463 g of the hydrochloride of -1-biphenylyl-. aminomethyl-ketone in 1620 cm3 of dimethyl-formamide, and. the mixture is mechanically stirred for about 3 hours. At the start of the reaction, the temperature rises to about 60 ° C. After reacting for 3 hours, the reaction mixture is poured, with stirring, into 8.33 liters of water and the mixture is further stirred for 1 hour.
The solid product is collected, washed with water and then with petroleum ether. If desired, we can purify it. .1-biphenylyl-dieMoracetamidom6thy-1-ketone thus obtained by recrystallization from ethyl acetate; point. fusion: 175-176 C.
This product meets the formula
EMI0002.0014
Example <I> II: </I> A mixture formed of 52 g of dichloroacetic acid and 56,
5 g of benzoyl chloride is added to 50 g of 4-biphenylyl-aminomethyl-ketone hydrochloride in 250 cm 3 of chlorbenzene. The reaction mixture is heated to 85 ° C. to initiate the reaction and to accelerate the formation of dichloroacetyl chloride by interaction of dichloroacetic acid and benzoyl chloride. The temperature of the reaction mixture is maintained for one hour at 85 ° C. and the temperature is then raised to 125 ° C. for half an hour.
Then the reaction mixture is filtered through. the hot state and the filtrate is left to cool. The insoluble 4-biphenylyl-cli-ehloracetamidomethyl ketone is collected and purified by recrystallization from ethyl acetate; melting point: 1.75-176 C.
Claims (1)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US302010XA | 1949-03-26 | 1949-03-26 | |
| CH297008T | 1950-02-15 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CH302010A true CH302010A (en) | 1954-09-30 |
Family
ID=25733728
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CH302010D CH302010A (en) | 1949-03-26 | 1950-02-15 | Process for preparing a 4-biphenylyl-acylamidomethyl-ketone. |
Country Status (1)
| Country | Link |
|---|---|
| CH (1) | CH302010A (en) |
-
1950
- 1950-02-15 CH CH302010D patent/CH302010A/en unknown
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