CH280830A - A process for the preparation of y, y-dicarbethoxy-caproaldehyde. - Google Patents
A process for the preparation of y, y-dicarbethoxy-caproaldehyde.Info
- Publication number
- CH280830A CH280830A CH280830DA CH280830A CH 280830 A CH280830 A CH 280830A CH 280830D A CH280830D A CH 280830DA CH 280830 A CH280830 A CH 280830A
- Authority
- CH
- Switzerland
- Prior art keywords
- caproaldehyde
- parts
- dicarbethoxy
- preparation
- pressure
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims description 4
- 238000002360 preparation method Methods 0.000 title claims description 3
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 4
- IYXGSMUGOJNHAZ-UHFFFAOYSA-N Ethyl malonate Chemical compound CCOC(=O)CC(=O)OCC IYXGSMUGOJNHAZ-UHFFFAOYSA-N 0.000 claims description 2
- 238000009835 boiling Methods 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 claims description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- VNDPUMWYEFWECV-UHFFFAOYSA-N 2-ethoxycarbonylbutanoic acid Chemical compound CCOC(=O)C(CC)C(O)=O VNDPUMWYEFWECV-UHFFFAOYSA-N 0.000 description 4
- 238000004821 distillation Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 229960000583 acetic acid Drugs 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000004508 fractional distillation Methods 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/66—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety
- C07C69/67—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety of saturated acids
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
Procédé de préparation de r,y-dicarbéthoxy-caproaldéhyde. La présente invention a pour objet un procédé de préparation de y,y-dicarbéthoxy- caproaldéhyde qui est un composé nouveau, particulièrement utile comme intermédiaire pour différentes synthèses organiques.
Suivant la présente invention, on prépare le @,,y-dicarbéthoxv-caproaldéhyde en faisant réagir de l'éthylmalonate d'éthyle avec de l'acroléine, en présence d'un catalyseur alca lin. On a constaté que, dans ces conditions, il se produit une addition d'éthylmalonate d'éthyle aux doubles liaisons de l'acroléine en 1,4.
Le produit d'addition en 1,4 subit ensuite une transformation et forme le y,y-dicarbé- thoxy-caproaldéhyde. Ces différentes réac tions sont représentées par le schéma sui vant:
EMI0001.0010
Le composé obtenu est un liquide incolore, présentant un point d'ébullition de 82 à 86 C sous une pression de 0,11 mm et un indice de réfraction nD30=1,4370.
De préférence, on effectue la réaction en présence d'un solvant organique.
Dans l'exemple suivant, les parties indi quées s'entendent en poids.
<I>Exemple:</I> Une solution alcoolique contenant 200 par ties d'alcool éthylique absolu, 0,04 partie de sodium et 75,1 parties d'éthylmalonate d'éthyle est refroidie à -1 C. De l'acroléine (23,5 parties) est. ajoutée en 45 minutes, à une vitesse telle que la température de la solution reste entre 0 et -4 C. Le mélange résultant est. agité, pendant une heure encore, dans un bain de glace, et ensuite placé dans un réfrigérateur pendant. 14 heures. Le cata lyseur est ensuite neutralisé par addition d'une partie d'acide acétique glacial.
L'alcool est chassé par distillation sous pression ré duite. L'huile résiduelle est reprise dans 400 parties de benzène et la solution benzé nique est lavée avec. de l'eau, et, séchée sur du sulfate de sodium anhydre. Le benzène est finalement enlevé par distillation soifs pres sion réduite.
Le poids de l'huile résiduelle, qui -est soumise à la. distillation fractionnée sous pression réduite,, est de 88,6 parties. La distillation fournit approximativement 67 parties de distillat qui passe entre 60 et 100 C à 0,2 mm. II reste 19 parties d'un résidu fortement visqueux. Le distillat est soumis à une nouvelle distillation sous pres sion réduite. On sépare cinq fractions.
La première fraction, recueillie à 47 à 54 C sous une pression de 0,1 mm, constitue 7 par ties en poids. Elle se compose essentiellement d'éthylmalonate d'éthyle.
La deuxième fraction qui est recueillie à une température comprise entre 54 et 70 C sous 0,08 mm de pression et qui foi-me envi ron 6 parties en poids est probablement un niélanae composé d'ester malonique n'ayant pas réagi et de l'aldéhyde désiré.
La troi sième fraction, recueillie à une température comprise entre 70 et 75 C sous 0,07 mm de pression, constitue 15 parties en poids et pré sente un indice de réfraction nD25=1,4372. La quatrième fraction, recueillie à une tem pérature comprise entre 75 à 75,5 C sous une pression de 0,07 mm, constitue environ 19 parties en poids et présente un indice de réfraction nD25=1,4386. La fraction N 5, recueillie à une température comprise entre 75,
5 et 77 C soirs une pression de 0,07 mm, constitue environ 16 parties en poids et pré sente un indice de réfraction nD25=1,4394. Les trois dernières fractions<B>(</B>3, 4 et.<B>5)</B> se composent essentiellement de ;,,y-dica.rbé- thoxy-caproaldéhyde. L'aldéhyde est earaeté- risé par sa 2,4-.dinitrophénylhydrazone qui est préparée de la manière habituelle. La dinitrophénylhydrazone purifiée fond à<B>100,5</B> à 101,5 C.
A process for preparing r, y-dicarbethoxy-caproaldehyde. The present invention relates to a process for the preparation of γ, y-dicarbethoxy-caproaldehyde which is a new compound, particularly useful as an intermediate for various organic syntheses.
According to the present invention, @ ,, y-dicarbethoxv-caproaldehyde is prepared by reacting ethyl ethylmalonate with acrolein in the presence of an alkaline catalyst. It has been found that, under these conditions, an addition of ethyl ethylmalonate occurs to the double bonds of the 1,4-acrolein.
The 1,4 adduct then undergoes conversion to form y, y-dicarbethoxy-caproaldehyde. These different reactions are represented by the following diagram:
EMI0001.0010
The compound obtained is a colorless liquid, exhibiting a boiling point of 82 to 86 C under a pressure of 0.11 mm and a refractive index nD30 = 1.4370.
Preferably, the reaction is carried out in the presence of an organic solvent.
In the following example, the parts indicated are by weight.
<I> Example: </I> An alcoholic solution containing 200 parts of absolute ethyl alcohol, 0.04 part of sodium and 75.1 parts of ethyl ethylmalonate is cooled to -1 C. Acrolein (23.5 parts) est. added over 45 minutes, at a rate such that the temperature of the solution remains between 0 and -4 C. The resulting mixture is. stirred for a further hour in an ice bath, and then placed in a refrigerator for. 14 hours. The catalytic converter is then neutralized by adding part of glacial acetic acid.
The alcohol is removed by distillation under reduced pressure. The residual oil is taken up in 400 parts of benzene and the benzene solution is washed with. water, and, dried over anhydrous sodium sulfate. The benzene is finally removed by distillation at reduced pressure.
The weight of the residual oil, which is subjected to the. Fractional distillation under reduced pressure is 88.6 parts. The distillation provides approximately 67 parts of distillate which passes between 60 and 100 C at 0.2 mm. 19 parts of a highly viscous residue remain. The distillate is subjected to further distillation under reduced pressure. Five fractions are separated.
The first fraction, collected at 47 to 54 ° C. under a pressure of 0.1 mm, constitutes 7 parts by weight. It consists mainly of ethyl ethylmalonate.
The second fraction which is collected at a temperature between 54 and 70 C under 0.08 mm of pressure and which is about 6 parts by weight is probably a nielanae composed of unreacted malonic ester and desired aldehyde.
The third fraction, collected at a temperature between 70 and 75 ° C. under 0.07 mm of pressure, constitutes 15 parts by weight and has a refractive index nD25 = 1.4372. The fourth fraction, collected at a temperature of between 75 to 75.5 C under a pressure of 0.07 mm, constitutes approximately 19 parts by weight and has a refractive index nD25 = 1.4386. Fraction N 5, collected at a temperature between 75,
5 and 77 ° C even at a pressure of 0.07 mm, constitutes about 16 parts by weight and has a refractive index nD25 = 1.4394. The last three fractions <B> (</B> 3, 4 and. <B> 5) </B> consist mainly of; ,, y-dica.rbeethoxy-caproaldehyde. The aldehyde is aerated by its 2,4-dinitrophenylhydrazone which is prepared in the usual manner. Purified dinitrophenylhydrazone melts at <B> 100.5 </B> at 101.5 C.
Claims (1)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US280830XA | 1946-12-06 | 1946-12-06 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CH280830A true CH280830A (en) | 1952-02-15 |
Family
ID=21841476
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CH280830D CH280830A (en) | 1946-12-06 | 1948-02-23 | A process for the preparation of y, y-dicarbethoxy-caproaldehyde. |
Country Status (1)
| Country | Link |
|---|---|
| CH (1) | CH280830A (en) |
-
1948
- 1948-02-23 CH CH280830D patent/CH280830A/en unknown
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