CH401969A - Process for obtaining a solution of a symmetrical organozinc - Google Patents
Process for obtaining a solution of a symmetrical organozincInfo
- Publication number
- CH401969A CH401969A CH631860A CH631860A CH401969A CH 401969 A CH401969 A CH 401969A CH 631860 A CH631860 A CH 631860A CH 631860 A CH631860 A CH 631860A CH 401969 A CH401969 A CH 401969A
- Authority
- CH
- Switzerland
- Prior art keywords
- solution
- dimethylformamide
- dimethylzinc
- obtaining
- organozinc
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 33
- AXAZMDOAUQTMOW-UHFFFAOYSA-N dimethylzinc Chemical compound C[Zn]C AXAZMDOAUQTMOW-UHFFFAOYSA-N 0.000 claims description 10
- -1 methylzinc halide Chemical class 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 2
- SOHOYYHPFIUFDH-UHFFFAOYSA-M [Br-].[Zn+]C Chemical compound [Br-].[Zn+]C SOHOYYHPFIUFDH-UHFFFAOYSA-M 0.000 claims 1
- GZUXJHMPEANEGY-UHFFFAOYSA-N bromomethane Chemical compound BrC GZUXJHMPEANEGY-UHFFFAOYSA-N 0.000 description 8
- 229940102396 methyl bromide Drugs 0.000 description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- KDUWXMIHHIVXER-UHFFFAOYSA-N 2'-hydroxypropiophenone Chemical compound CCC(=O)C1=CC=CC=C1O KDUWXMIHHIVXER-UHFFFAOYSA-N 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- WBJINCZRORDGAQ-UHFFFAOYSA-N formic acid ethyl ester Natural products CCOC=O WBJINCZRORDGAQ-UHFFFAOYSA-N 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 description 1
- ABJKIHHNDMEBNA-UHFFFAOYSA-N methylchromone Chemical compound C1=CC=C2C(=O)C(C)=COC2=C1 ABJKIHHNDMEBNA-UHFFFAOYSA-N 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- NMLXKNNXODLJIN-UHFFFAOYSA-M zinc;carbanide;chloride Chemical compound [CH3-].[Zn+]Cl NMLXKNNXODLJIN-UHFFFAOYSA-M 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
- C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D311/04—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring
- C07D311/22—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 4
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F3/00—Compounds containing elements of Groups 2 or 12 of the Periodic Table
- C07F3/06—Zinc compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
Procédé d'obtention de solution d'un organozincique symétrique
La présente invention a pour objet un procédé d'obtention de solutions de diméthylzinc dans le
N,N-diméthylformamide.
On sait que le diméthylzinc est un réactif difficile à manier étant donné qu'il s'enflamme spontanément à l'air.
Or, il a été trouvé à présent que le diméthylzinc en solution dans le N,N-diméthylformamide peut être manipulé sans danger à l'air.
Les solutions de diméthylzinc dans le N,N-diméthylformamide constituent des réactifs utiles pour la synthèse organique et trouvent leur application, par exemple, dans la préparation de la 3-méthylchromone à partir de l'o-hydroxypropiophénone et du formiate d'éthyle.
Le procédé d'obtention de ces solutions de diméthylzinc suivant l'invention consiste à chauffer sous pression réduite une solution d'un halogénure de méthylzinc dans le N,N-diméthylformamide pour obtenir, comme distillat, la solution de diméthylzinc dans le N,N-diméthylformamide.
La préparation de l'halogénure de méthylzinc peut être effectuée selon le procédé décrit dans le brevet suisse No 412433.
Dans l'exemple suivant, les températures sont indiquées en degrés centigrades.
Exemple
On mélange 400 g de zinc (poudre, feuilles, copeaux, etc.) avec 300 cm3 de N,N-diméthylformamide et 5 cm3 d'iodure de méthyle et fait arriver un faible courant de bromure de méthyle. La température s'élève en 15 mn à 5O55o C. La réaction démarre alors d'une manière assez vive et l'on refroidit par un bain d'eau glacée. Après quelques minutes, on accélère le débit de bromure de méthyle et on introduit en une demi-heure, tout en maintenant la température à 45-500 C, 700 cm3 de N,N-diméthylform- amide. On continue l'introduction du bromure de méthyle toujours à 45-500 C jusqu'à disparition com plète du zinc, ce qui demande 3 heures environ. Vers la fin de l'opération, la réaction n'étant plus suffisamment exothermique, on chauffe pour maintenir la température constante.
La solution est ensuite distillée sous vide (17 mm Hg). Le léger excès de bromure de méthyle présent dans le mélange réactionnel est éliminé puis le mélange N,N-diméthylform- amide-diméthylzinc distille. On recueille séparément les fractions qui distillent jusqu'à 60-630 C, puis de 60-630 à 700 C environ.
La première fraction, solution limpide et incolore, pèse 770 à 775 g et contient 3 à 3,2 molécules de diméthylzinc par kilo de solution. La seconde fraction pèse 260 à 2165 g et contient 1,2 à 1,4 molécule de diméthylzinc par kilo. Rendement global à partir du zinc: 87 à 93 /o.
On prépare d'une manière analogue le diméthylzinc à partir d'iodure ou de chlorure de méthylzinc dans le N,N-diméthylformamide.
Process for obtaining a solution of a symmetrical organozinc
The present invention relates to a process for obtaining solutions of dimethylzinc in the
N, N-dimethylformamide.
Dimethylzinc is known to be a difficult reagent to handle since it ignites spontaneously in air.
However, it has now been found that dimethylzinc in solution in N, N-dimethylformamide can be handled without danger in air.
Solutions of dimethylzinc in N, N-dimethylformamide are useful reagents for organic synthesis and find application, for example, in the preparation of 3-methylchromone from o-hydroxypropiophenone and ethyl formate.
The process for obtaining these dimethylzinc solutions according to the invention consists in heating under reduced pressure a solution of a methylzinc halide in N, N-dimethylformamide to obtain, as distillate, the solution of dimethylzinc in N, N -dimethylformamide.
The preparation of the methylzinc halide can be carried out according to the process described in Swiss Patent No. 412433.
In the following example, temperatures are shown in degrees centigrade.
Example
400 g of zinc (powder, sheets, shavings, etc.) are mixed with 300 cm3 of N, N-dimethylformamide and 5 cm3 of methyl iodide and a weak stream of methyl bromide is introduced. The temperature rises in 15 min to 5055 ° C. The reaction then starts quite vigorously and it is cooled by an ice-water bath. After a few minutes, the flow of methyl bromide is accelerated and the mixture is introduced in half an hour, while maintaining the temperature at 45-500 C, 700 cm3 of N, N-dimethylform-amide. The introduction of methyl bromide is continued, still at 45-500 ° C. until complete disappearance of the zinc, which requires approximately 3 hours. Towards the end of the operation, the reaction no longer being sufficiently exothermic, it is heated to maintain the temperature constant.
The solution is then distilled under vacuum (17 mm Hg). The slight excess of methyl bromide present in the reaction mixture is removed and then the N, N-dimethylform-amide-dimethylzinc mixture is distilled off. The fractions which distill up to 60-630 C and then from 60-630 to 700 C approximately are collected separately.
The first fraction, a clear and colorless solution, weighs 770 to 775 g and contains 3 to 3.2 molecules of dimethylzinc per kilo of solution. The second fraction weighs 260 to 2165 g and contains 1.2 to 1.4 molecules of dimethylzinc per kilo. Overall yield from zinc: 87 to 93 / o.
Dimethylzinc is prepared in an analogous manner from iodide or methylzinc chloride in N, N-dimethylformamide.
Claims (1)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR796687A FR1236116A (en) | 1959-06-05 | 1959-06-05 | Solutions of a symmetrical organozinc and their obtaining |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CH401969A true CH401969A (en) | 1965-11-15 |
Family
ID=8715667
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CH631860A CH401969A (en) | 1959-06-05 | 1960-06-02 | Process for obtaining a solution of a symmetrical organozinc |
Country Status (3)
| Country | Link |
|---|---|
| CH (1) | CH401969A (en) |
| ES (1) | ES258431A1 (en) |
| FR (1) | FR1236116A (en) |
-
1959
- 1959-06-05 FR FR796687A patent/FR1236116A/en not_active Expired
-
1960
- 1960-05-28 ES ES0258431A patent/ES258431A1/en not_active Expired
- 1960-06-02 CH CH631860A patent/CH401969A/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| FR1236116A (en) | 1960-07-15 |
| ES258431A1 (en) | 1960-08-16 |
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