CH276548A - Process for the manufacture of the semi-carbazone of 5-nitro-2-furaldehyde. - Google Patents
Process for the manufacture of the semi-carbazone of 5-nitro-2-furaldehyde.Info
- Publication number
- CH276548A CH276548A CH276548DA CH276548A CH 276548 A CH276548 A CH 276548A CH 276548D A CH276548D A CH 276548DA CH 276548 A CH276548 A CH 276548A
- Authority
- CH
- Switzerland
- Prior art keywords
- semi
- acid
- nitro
- sub
- furaldehyde
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims description 13
- 150000007659 semicarbazones Chemical class 0.000 title claims description 4
- SXINBFXPADXIEY-UHFFFAOYSA-N 5-Nitrofurfural Chemical compound [O-][N+](=O)C1=CC=C(C=O)O1 SXINBFXPADXIEY-UHFFFAOYSA-N 0.000 title description 9
- 238000004519 manufacturing process Methods 0.000 title description 4
- 239000002253 acid Substances 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- UJTTUOLQLCQZEA-UHFFFAOYSA-N 9h-fluoren-9-ylmethyl n-(4-hydroxybutyl)carbamate Chemical compound C1=CC=C2C(COC(=O)NCCCCO)C3=CC=CC=C3C2=C1 UJTTUOLQLCQZEA-UHFFFAOYSA-N 0.000 claims description 6
- WJYYUEQVECTILJ-UHFFFAOYSA-N 1,4-diiodo-2,5-dimethylbenzene Chemical compound CC1=CC(I)=C(C)C=C1I WJYYUEQVECTILJ-UHFFFAOYSA-N 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 5
- 235000019441 ethanol Nutrition 0.000 claims description 5
- 238000002360 preparation method Methods 0.000 claims description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 2
- 239000011707 mineral Substances 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 description 8
- 230000007062 hydrolysis Effects 0.000 description 5
- 238000006460 hydrolysis reaction Methods 0.000 description 5
- 239000011541 reaction mixture Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- LPYIXHHGKPBPCF-UHFFFAOYSA-N acetic acid;5-nitrofuran-2-carbaldehyde Chemical compound CC(O)=O.CC(O)=O.[O-][N+](=O)C1=CC=C(C=O)O1 LPYIXHHGKPBPCF-UHFFFAOYSA-N 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- -1 aldehydes semicarbazones Chemical class 0.000 description 1
- 150000001540 azides Chemical class 0.000 description 1
- 239000008366 buffered solution Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/56—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D307/70—Nitro radicals
- C07D307/71—Nitro radicals attached in position 5
- C07D307/72—Nitro radicals attached in position 5 with hydrocarbon radicals, substituted by nitrogen-containing radicals, attached in position 2
- C07D307/74—Nitro radicals attached in position 5 with hydrocarbon radicals, substituted by nitrogen-containing radicals, attached in position 2 by hydrazino or hydrazono or such substituted radicals
- C07D307/76—Nitro radicals attached in position 5 with hydrocarbon radicals, substituted by nitrogen-containing radicals, attached in position 2 by hydrazino or hydrazono or such substituted radicals having carbonic acyl radicals or their thio or nitrogen analogues directly attached to the hydrazino or hydrazono radical, e.g. semicarbazides
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
Procédé pour la fabrication de la semi-carbazone de la 5-nitro-2-furaldéhyde. r La présente invention se rapporte à un procédé perfectionné de fabrication de la semi- carbazone de la 5-nitro-2-furaldéhyde.
Dans le passé, les semi-carbazones d'aldé hydes ont été préparées en faisant réagir l'aldéhyde sur le chlorhydrate de semi-carba- zide en solution tamponnée à l'aide d'un sel, tel que l'acétate de sodium.
L'application de ce procédé à la fabrication dé la 5-nitro-2- furaldéhyde semi-carbazone nécessite donc la préparation de la 5-nitro 2-furaldéhyde. Cette préparation s'effectue habituellement par hy drolyse du diacétate de 5-nitrofurfural.
La préparation du diacétate de 5-nitro- furfural est connue (voir Gilman et Wright, J.A.C:S. 52: 2550, 4165<B>[19301).</B> L'hydrolyse de cette matière est décrite par Gilman dans J.A.C.S. 52: 2552 (1930).
Cette hydrolyse im- plique l'emploi d'acide sulfurique à 30 % à température élevée en présence d'un courant du gaz carbonique, l'extraction du produit de l'hydrolyse avec des quantités relativement importantes d'éther, le séchage des extraits éthérés et l'élimination du solvant par distilla tion.
On obtient un produit impur brun-noir qu'il faut purifier par distillation et cristalli sation du distillat dans -des conditions très soigneusement contrôlées. Le rendement est d'environ 75 0/0.
On a découvert que le diacétate :de 5-nitro- furfural réagit directement .avec le .chlorhy drate de semi-carbazide avec formation de la semi-carbazone de la 5-nitro-2-furaldéhyde. L'opération d'hydrolyse intermédiaire peut donc être omise.
Le procédé de préparation de la semi-.car- bazone de la 5-nitro-2-furaldéhyde suivant l'invention est donc caractérisé en ce qu'on fait réagir du dia.cétate de 5-nitrofurfural di rectement avec du chlorhydrate de semi-car- b:azide.
Afin d'obtenir de la semi-carbazone de 5 nitro-2-furaldéhy de présentant un degré de pureté suffisant pour répondre aux exigences de l'emploi pharmaceutique, il est indiqué d'effectuer la réaction en présence -d'un acide minéral fort. Cet acide est, de préférence, de l'acide sulfurique, bien qu'on puisse égale ment utiliser de l'acide nitrique, de l'acide chlorhydrique ou de l'acide phosphorique.
La concentration en acide dans le mélange réactionnel peut être très faible. On a trouvé que l'on pouvait aisément effectuer la réaction avec une quantité de 1% d'acide seulement. Dans l'exemple qui suit, cette quantité d'acide produirait un pH d'environ 1,0 dans la solu tion primitive.
On préfère toutefois utiliser environ 5 % d'acide. Cette quantité abaisse le pH à .environ 0,4, dans l'exemple mentionné.
Dans ,la. mise en oeuvre du procédé, on pré pare, de préférence, premièrement une solu tion de chlorhydrate de semi-carbazide dans de l'eau contenant l'acide et on ajoute ensuite le diacét.ate de 5-nitro--2-furaldéhyde à cette solution. On chauffe le mélange, en agitant, jusqu'à une température comprise entre 80 et 90 C, à laquelle la réaction commence. Après le démarrage, la réaction se poursuit jusqu'à, achèvement saros qu'il soit nécessaire de chauf fer.
La réaction peut être amorcée à une tem pérature .supérieure à 90 C, mais elle est alors trop violente pour en permettre un contrôle facile. A la fin de la réaction la température du mélange réactionnel tombe au-dessous de 75 C. Le mélange réactionnel peut alors être refroidi et filtré.
On a constaté que la. préparation de la so lution réactionnelle est facilitée par l'addition à l'eau ,d'une certaine quantité d'alcool éthyli que. L'addition d'environ une partie d'alcool éthylique pour 8 parties d'eau employée donne de bons résultats.
<I>Exemple:</I> Dans un flacon à. fond rond à 3 tubulures, d'une capacité de 5 ,litres et muni d'un agita teur, d'un thermomètre et d'un réfrigérant. à reflux, on place 1700 ml d'eau, 200 ml d'alcool éthylique et 100 ml (184,0 g) d'acide sulfurique. A ,cette solution on :ajoute 111,5 g -de chlorhydrate de semi-carbazide et 243 g de diacétat.e de 5-nitro-furfural. On met l'agi tateur en route et on chauffe le flacon sur un bain de vapeur jusqu'à ce que la température du mélange réactionnel atteigne 85 C. L'arri vée de vapeur est alors coupée :et on laisse la.
réaction se faire, sous agitation constante, jus qu'à ce que la température tombe au-dessous de 75 C (1 heure). Le mélange réactionnel est refroidi en agitant, jusqu'à 20 C et filtré par aspiration. Les cristaux sont lavés sur le filtre par gravité avec 800 ml d'eau froide, puis avec 200 ml d'alcool éthylique. Les cris- taux sont séchés par aspiration sur le filtre pendant 1 Y h., puis pendant une nuit à 50 C. On obtient 194 de semi-carbazone, soit un rendement de 98 %.
Process for the manufacture of the semi-carbazone of 5-nitro-2-furaldehyde. The present invention relates to an improved process for making the semi-carbazon of 5-nitro-2-furaldehyde.
In the past, aldehydes semicarbazones have been prepared by reacting the aldehyde with semicarbazide hydrochloride in buffered solution with a salt, such as sodium acetate.
The application of this process to the manufacture of 5-nitro-2-furaldehyde semi-carbazone therefore requires the preparation of 5-nitro 2-furaldehyde. This preparation is usually carried out by hydrolysis of 5-nitrofurfural diacetate.
The preparation of 5-nitro-furfural diacetate is known (see Gilman and Wright, J.A.C: S. 52: 2550, 4165 <B> [19301). </B> The hydrolysis of this material is described by Gilman in J.A.C.S. 52: 2552 (1930).
This hydrolysis involves the use of 30% sulfuric acid at elevated temperature in the presence of a stream of carbon dioxide, the extraction of the hydrolysis product with relatively large quantities of ether, the drying of the extracts. ethereal compounds and the removal of the solvent by distillation.
An impure brown-black product is obtained which must be purified by distillation and crystallization of the distillate under very carefully controlled conditions. The yield is about 75%.
It has been found that 5-nitro-furfural diacetate reacts directly with the semi-carbazid chloridate to form the semi-carbazone of 5-nitro-2-furaldehyde. The intermediate hydrolysis operation can therefore be omitted.
The process for preparing the semi-carbonazone of 5-nitro-2-furaldehyde according to the invention is therefore characterized in that 5-nitrofurfural dia.cetate is reacted directly with semi-hydrochloride. -car- b: azide.
In order to obtain 5-nitro-2-furaldehyde semi-carbazon having a sufficient degree of purity to meet the requirements of pharmaceutical use, it is advisable to carry out the reaction in the presence of a strong mineral acid. . This acid is preferably sulfuric acid, although nitric acid, hydrochloric acid or phosphoric acid can also be used.
The concentration of acid in the reaction mixture can be very low. It has been found that the reaction can easily be carried out with an amount of only 1% acid. In the example which follows, this amount of acid would produce a pH of about 1.0 in the original solution.
However, it is preferred to use about 5% acid. This amount lowers the pH to about 0.4, in the example mentioned.
In the. In carrying out the process, a solution of semi-carbazide hydrochloride in water containing the acid is preferably prepared first and then 5-nitro - 2-furaldehyde diacetate is added to this solution. The mixture is heated, with stirring, to a temperature between 80 and 90 C, at which the reaction begins. After start-up, the reaction continues until completion if it is necessary to heat the iron.
The reaction can be initiated at a temperature above 90 ° C., but it is then too violent to allow easy control. At the end of the reaction the temperature of the reaction mixture drops below 75 ° C. The reaction mixture can then be cooled and filtered.
It was found that the. Preparation of the reaction solution is facilitated by the addition to water of a certain quantity of ethyl alcohol. The addition of about one part of ethyl alcohol to 8 parts of water employed gives good results.
<I> Example: </I> In a. round bottom with 3 tubes, with a capacity of 5.1 liters and equipped with a stirrer, a thermometer and a condenser. at reflux, 1700 ml of water, 200 ml of ethyl alcohol and 100 ml (184.0 g) of sulfuric acid are placed. To this solution are added 111.5 g of semi-carbazide hydrochloride and 243 g of 5-nitro-furfural diacétat.e. The stirrer is started and the flask is heated on a steam bath until the temperature of the reaction mixture reaches 85 C. The steam supply is then cut off: and it is left there.
The reaction proceeds, with constant stirring, until the temperature drops below 75 C (1 hour). The reaction mixture is cooled with stirring, to 20 ° C. and filtered with suction. The crystals are washed on the filter by gravity with 800 ml of cold water, then with 200 ml of ethyl alcohol. The crystals are dried by suction on the filter for 1 hour, then overnight at 50 ° C. 194 of semi-carbon dioxide are obtained, ie a yield of 98%.
Claims (1)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US276548XA | 1946-07-19 | 1946-07-19 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CH276548A true CH276548A (en) | 1951-07-15 |
Family
ID=21839007
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CH276548D CH276548A (en) | 1946-07-19 | 1947-07-18 | Process for the manufacture of the semi-carbazone of 5-nitro-2-furaldehyde. |
Country Status (1)
| Country | Link |
|---|---|
| CH (1) | CH276548A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1045417B (en) * | 1956-04-09 | 1958-12-04 | Norwich Pharma Co | Process for the preparation of 5-nitrofurfurol- (p-arsenophenyl) -semicarbazone and its alkali or ammonium salts |
-
1947
- 1947-07-18 CH CH276548D patent/CH276548A/en unknown
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1045417B (en) * | 1956-04-09 | 1958-12-04 | Norwich Pharma Co | Process for the preparation of 5-nitrofurfurol- (p-arsenophenyl) -semicarbazone and its alkali or ammonium salts |
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