CH156108A - Process for preparing an artificial musk. - Google Patents
Process for preparing an artificial musk.Info
- Publication number
- CH156108A CH156108A CH156108DA CH156108A CH 156108 A CH156108 A CH 156108A CH 156108D A CH156108D A CH 156108DA CH 156108 A CH156108 A CH 156108A
- Authority
- CH
- Switzerland
- Prior art keywords
- butylparacymene
- tertiary
- paracymene
- nitration
- treating
- Prior art date
Links
- JHGWQSGWUPCKNT-UHFFFAOYSA-N 2-tert-butyl-4-methyl-1,3,5-trinitrobenzene Chemical compound CC1=C([N+]([O-])=O)C=C([N+]([O-])=O)C(C(C)(C)C)=C1[N+]([O-])=O JHGWQSGWUPCKNT-UHFFFAOYSA-N 0.000 title claims description 3
- 238000004519 manufacturing process Methods 0.000 title claims 2
- IEZIVCUMBDFNQN-UHFFFAOYSA-N 2-butyl-4-methyl-1-propan-2-ylbenzene Chemical group C(CCC)C1=C(C=CC(=C1)C)C(C)C IEZIVCUMBDFNQN-UHFFFAOYSA-N 0.000 claims description 11
- 238000006396 nitration reaction Methods 0.000 claims description 11
- HFPZCAJZSCWRBC-UHFFFAOYSA-N p-cymene Chemical compound CC(C)C1=CC=C(C)C=C1 HFPZCAJZSCWRBC-UHFFFAOYSA-N 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 7
- 241000402754 Erythranthe moschata Species 0.000 claims description 6
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 6
- BMMRJSDWXNGOJI-UHFFFAOYSA-N 4-tert-butyl-2-methyl-1,3-dinitro-5-propan-2-ylbenzene Chemical compound CC(C)C1=CC([N+]([O-])=O)=C(C)C([N+]([O-])=O)=C1C(C)(C)C BMMRJSDWXNGOJI-UHFFFAOYSA-N 0.000 claims description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 5
- 230000006208 butylation Effects 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 4
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 3
- 235000002783 ambrette Nutrition 0.000 claims description 3
- 244000096712 ambrette Species 0.000 claims description 3
- 239000013078 crystal Substances 0.000 claims description 3
- 238000002425 crystallisation Methods 0.000 claims description 3
- 230000008025 crystallization Effects 0.000 claims description 3
- 238000002844 melting Methods 0.000 claims description 3
- 230000008018 melting Effects 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 239000000470 constituent Substances 0.000 claims description 2
- QTBFPMKWQKYFLR-UHFFFAOYSA-N isobutyl chloride Chemical compound CC(C)CCl QTBFPMKWQKYFLR-UHFFFAOYSA-N 0.000 claims description 2
- 239000007937 lozenge Substances 0.000 claims description 2
- NBRKLOOSMBRFMH-UHFFFAOYSA-N tert-butyl chloride Chemical compound CC(C)(C)Cl NBRKLOOSMBRFMH-UHFFFAOYSA-N 0.000 claims description 2
- 238000009835 boiling Methods 0.000 claims 1
- 239000007788 liquid Substances 0.000 claims 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 229940028444 muse Drugs 0.000 description 3
- GMVPRGQOIOIIMI-DWKJAMRDSA-N prostaglandin E1 Chemical compound CCCCC[C@H](O)\C=C\[C@H]1[C@H](O)CC(=O)[C@@H]1CCCCCCC(O)=O GMVPRGQOIOIIMI-DWKJAMRDSA-N 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical class CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical class N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000009965 odorless effect Effects 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Chemical group 0.000 description 1
- YBBRCQOCSYXUOC-UHFFFAOYSA-N sulfuryl dichloride Chemical compound ClS(Cl)(=O)=O YBBRCQOCSYXUOC-UHFFFAOYSA-N 0.000 description 1
- 150000003613 toluenes Chemical class 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
Procédé de préparation d'un muse artificiel. Il est connu qu'on obtient .des produits à odeur de musc par nitration des dérivés du toluène qui contiennent un substituant iso- propyle ou isobutyle ou isoamyle .et qu'on obtient une odeur différente en introduisant dans ces hydrocarbures des substituants halo gènes ou des radicaux organiques tels que CN, CHO, COCHS, OCHs.
On a trouvé qu'on obtient -des produits à odeur de musc d'une note différente de celle des muscs commerciaux actuellement connus, par nitration d'hydrocarbures dérivés du -to luène qui contiennent simultanément les groupes isopropyle et butyle tertiaire.
Ainsi par nitration des tertiaires butyl- cymènes, substances inconnues à ce jour, et dont la préparation est décrite plus loin, on obtient des produits à odeur de muse qui peu vent être utilisés en parfumerie.
La présente invention conêerne précisé ment un procédé pour la préparation d'un musc artificiel, qui est caractérisé en ce que l'on soumet à la nitration du tertiaire butyl- paracymène obtenu par butylation de para- cymène et en ce que l'on purifie le dinitro- tertiaire-butylparacymène obtenu par cristal lisation répétée.
Le dinitro-tertiaire-butylparacymène ainsi obtenu se présente sous forme de cristaux en losanges, jaune-clair, à point de fusion 13? à 133', solubles dans l'alcool et qui possè dent une intense odeur de musc rappelant celle de la graine d'ambrette. Il est caracté risé par la présence simultanée des fonc tions isopropyle et butyle tertiaire dans sa formule de constitution; son odeur de muse d'une note nouvelle permet son emploi en parfumerie.
La nitration -du tertiaire-butylparacymène peut être réalisée à l'aide d'acide nitrique fumant ou d'un mélange sulfonitrique.
La butylation du paracymène peut être effectuée en traitant ce dernier avec -de l'al cool butylique tertiaire, en présence d'acide, sulfurique ou de chlorure de zinc. On peut également effectuer cette butylation en trai tant le paracymène, en présence de chlorure d'aluminium, avec Uu chlorure de butyle tertiaire ou encore avec du chlorure d'isobu- tyle. On pourrait supposer qu'avec ce der nier corps il se formera de l'isobutylparacy- rnène, mais ce n'est pas le cas,
l'expérience a montré qu'il se forme 4u tertiaire butyl- paracymène comme dans les deux autres cas indiqués. C'est cependant le traitement du paracymène par l'alcool butylique tertiaire, en présence d'acide sulfurique, qui donne le meilleur rendement.
Le tertiaire butylparacymène peut être préparé, par exemple, comme suit: 200 kg d'acide sulfurique concentré ordi naire sont refroidis à - 5 , et, en agitant, on coule dans l'acide 80 kg de paracymène, puis 16 kg d'alcool butylique tertiaire sans lais ser la température du mélange dépasser 0 . Le mélange est ensuite coulé dans de l'eau glacée, la couche supérieure est séparée, neu tralisée avec de la soude caustique et on dis tille.
On récupère une certaine quantité de paracymène qui est portée à une opération suivante et la fraction qui passe entre 220 et 230 constitue le tertiaire butylparacymène.
Selon la présente invention, on soumet à la nitration ce tertiaire hutylparacymène dans de l'acide nitrique fumant ou dans le mélange sulfonitrique pour en obtenir le dérivé dini- tré. Dans l'acide nitrique à 70 % , on n'ob tient que le dérivé mononitré qui est sans odeur.
-Voici, par exemple, comment on peut pro céder pour effectuer la nitration selon le pro cédé de l'invention: 100 kg d'acide nitrique fumant (92 à 95 ô ) sont refroidis dans un bain réfrigérant et sous constante agitation on coule lentement 15 kg de tertiaire butylparacymène en ayant soin que la température du mélange ne dé passe pas -f- 5 C. Le mélange est ensuite versé dans de l'eau glacée, le produit nitré, qui se sépare à l'état cristallin, est essoré, lavé à l'eau, puis à l'eau alcaline et purifié par cristallisation dans l'alcool ou dans un autre solvant.
On peut remplacer, pour raison d'écono mie, l'acide nitrique par un mélange d'acides sulfurique .et nitrique.
Le dinitro-tertiaire-butylparacymène se présente sous forme de cristaux en losanges, jaune-clair, à point de fusion 1.32 à 13,3 0 et qui possèdent une intense odeur de musc qui rappelle celle de la graine d'ambrette.
Method of preparing an artificial muse. It is known that products with a musk odor are obtained by nitration of toluene derivatives which contain an isopropyl or isobutyl or isoamyl substituent and that a different odor is obtained by introducing into these hydrocarbons halogen substituents or organic radicals such as CN, CHO, COCHS, OCHs.
It has been found that products with a musk odor of a different note from that of currently known commercial musks are obtained by nitration of hydrocarbons derived from -to luene which simultaneously contain isopropyl and tertiary butyl groups.
Thus, by nitration of tertiary butylcymenes, substances unknown to date, the preparation of which is described below, products with a muse odor are obtained which can be used in perfumery.
The present invention relates specifically to a process for the preparation of an artificial musk, which is characterized in that the tertiary butyl-paracymene obtained by butylation of paracymene is subjected to nitration and in that it is purified. dinitro-tertiary-butylparacymene obtained by repeated crystallization.
The dinitro-tertiary-butylparacymene thus obtained is in the form of lozenge crystals, light yellow, melting point 13? at 133 ', soluble in alcohol and which has an intense musk odor reminiscent of ambrette seed. It is characterized by the simultaneous presence of isopropyl and tertiary butyl functions in its constituent formula; its muse smell with a new note allows its use in perfumery.
Nitration -du tertiary-butylparacymene can be carried out using fuming nitric acid or a sulfonitric mixture.
The butylation of paracymene can be carried out by treating the latter with tertiary butyl alcohol in the presence of acid, sulfuric or zinc chloride. This butylation can also be carried out by treating the paracymene, in the presence of aluminum chloride, with tertiary butyl chloride or alternatively with isobutyl chloride. One might suppose that with this latter body there will be formed isobutylparacy- rnene, but this is not the case,
experience has shown that tertiary butyl-paracymene is formed as in the other two cases indicated. However, it is the treatment of paracymene with tertiary butyl alcohol, in the presence of sulfuric acid, which gives the best yield.
Tertiary butylparacymene can be prepared, for example, as follows: 200 kg of ordinary concentrated sulfuric acid are cooled to - 5, and, with stirring, 80 kg of paracymene are poured into the acid, then 16 kg of alcohol tertiary butyl without allowing the temperature of the mixture to exceed 0. The mixture is then poured into ice water, the upper layer is separated, neutralized with caustic soda and distilled.
A certain quantity of paracymene is recovered which is taken to a following operation and the fraction which passes between 220 and 230 constitutes the tertiary butylparacymene.
According to the present invention, this tertiary hutylparacymene is subjected to nitration in fuming nitric acid or in the sulphonitric mixture to obtain the dinitrogen derivative. In 70% nitric acid, only the mononitrated derivative which is odorless is obtained.
-Here, for example, how one can proceed to carry out the nitration according to the process of the invention: 100 kg of fuming nitric acid (92 to 95 ô) are cooled in a cooling bath and with constant stirring, slowly poured 15 kg of tertiary butylparacymene, taking care that the temperature of the mixture does not exceed -f- 5 C. The mixture is then poured into ice-cold water, the nitrated product, which separates in the crystalline state, is drained. , washed with water, then with alkaline water and purified by crystallization from alcohol or from another solvent.
Nitric acid can be replaced, for reasons of economy, by a mixture of sulfuric and nitric acids.
Dinitro-tertiary-butylparacymene occurs in the form of diamond-shaped crystals, light yellow, with a melting point of 1.32 to 13.3 0 and which have an intense musk odor reminiscent of that of ambrette seed.
Claims (1)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE156108X | 1930-04-12 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CH156108A true CH156108A (en) | 1932-07-31 |
Family
ID=5677549
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CH156108D CH156108A (en) | 1930-04-12 | 1931-01-28 | Process for preparing an artificial musk. |
Country Status (1)
| Country | Link |
|---|---|
| CH (1) | CH156108A (en) |
-
1931
- 1931-01-28 CH CH156108D patent/CH156108A/en unknown
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