EP0006616B1 - Tiglic acid ester, process for its preparation, its application and compositions containing it - Google Patents

Tiglic acid ester, process for its preparation, its application and compositions containing it Download PDF

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Publication number
EP0006616B1
EP0006616B1 EP79102139A EP79102139A EP0006616B1 EP 0006616 B1 EP0006616 B1 EP 0006616B1 EP 79102139 A EP79102139 A EP 79102139A EP 79102139 A EP79102139 A EP 79102139A EP 0006616 B1 EP0006616 B1 EP 0006616B1
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Prior art keywords
methyl
buten
compositions
tiglate
tiglic acid
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German (de)
French (fr)
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EP0006616A1 (en
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Roman Kaiser
Dietmar Dr. Lamparsky
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Givaudan SA
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L Givaudan and Co SA
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    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
    • C11B9/00—Essential oils; Perfumes
    • C11B9/0007—Aliphatic compounds
    • C11B9/0015—Aliphatic compounds containing oxygen as the only heteroatom
    • C11B9/0019—Aliphatic compounds containing oxygen as the only heteroatom carbocylic acids; Salts or esters thereof

Definitions

  • the invention relates to a new fragrance and / or flavor. It is the compound of the formula So the 2-methyl-2-buten-1-yltiglate.
  • the invention further relates to a process for the preparation of the compound of the formula
  • This process is characterized in that 2-methyl-2-buten-1-o1 is esterified with tiglinic acid or a reactive derivative thereof, that one transesterifies a tiglinic acid lower alkyl ester with 2-methyl-2-buten-1-ol, or that a 2-methyl-2-buten-1-yl halide with an alkali metal salt of tiglinic acid.
  • esterification of tiglinic acid or its derivative can be carried out according to methods known per se, for example according to Table I (see also "Organikum”, Org. Chem. Grundpraktikum, VEB Deutscher Verlag dermaschineen, Berlin 1969, 9th edition, p . 440 ff).
  • the tiglinic acid lower alkyl ester used is in particular the methyl or the ethyl ester, since the low-boiling alcohols formed in the reaction, methanol or ethanol, can thus be easily distilled off.
  • the compound I has special organoleptic properties, on the basis of which it is particularly suitable as a fragrance and / or flavoring.
  • the invention accordingly also relates to the use of the compound I as a fragrance and / or flavoring.
  • the compound I used according to the invention as a fragrance and / or flavoring is distinguished by an original smell which is very surprising for an ester of this carbon number. This can be described as follows: pronounced of damp forest soil, mushroom-like (mushroom), slightly anise-like, flowery, soft, with aspects of the smell of young leaf buds. What is striking is the complete absence of the fruity note and the appearance of nuances to be classified as floral and the emergence of the natural forest floor character.
  • the compound I can be used, for example, for perfuming or aromatizing products, such as cosmetics (soaps, ointments, powders, toothpastes, mouthwashes, deodorants, shampoos, lotions, etc.), detergents, or foods, luxury foods and beverages
  • the Compound I is preferably not used alone, but in the form of compositions with other fragrances or flavors.
  • Such fragrance or flavoring compositions with a content of I and their preparation in a manner known per se (addition of I to known fragrance or flavoring compositions or mixing of I with natural or synthetic compounds suitable as a component of fragrance or flavoring compositions or Mixtures) also form the subject of the invention.
  • fragrances listed above can be used in a manner known to the perfumer, e.g. from W. A. Poucher, Perfumes, Cosmetics and Soaps 2, 7th edition, Chapman and Hall, London, 1974.
  • the concentration of compound 1 can vary within wide limits, depending on the intended use, for example between about 0.01 (detergents) and about 15% by weight (alcoholic solutions).
  • concentrations in perfume bases or concentrates can of course also be higher.
  • the perfume bases can be used in the usual way for perfuming Eaux de Cologne, Eux de toilette, tincts, lotions, creams, shampoos, soaps and detergents, etc.
  • the use of I in colognes and in tincts is preferred.
  • a flavoring compound I can be used, for example, to produce or improve, enhance, increase or modify various types of aromatics, such as these e.g. for flavoring foods (yogurt, sweets etc.), luxury foods (tea etc.) and beverages (lemonades etc.).
  • aromatics such as these e.g. for flavoring foods (yogurt, sweets etc.), luxury foods (tea etc.) and beverages (lemonades etc.).
  • interesting effects in the modification of strawberry or herbal tea aromas can be achieved by adding I; see table II.
  • a suitable dosage includes, for example, the range from 0.1 ppm-100 ppm, preferably from 1 ppm-20 ppm in the finished product, i.e. the flavored food, luxury food or drink.
  • the compound can be mixed in a conventional manner with the constituents used for flavoring compositions or added to such flavors.
  • the aromas used according to the invention are understood to mean flavoring compositions which can be diluted in a manner known per se or distributed in edible materials. They can be converted into the usual forms of use, such as solutions, pastes or powders, using methods known per se.
  • the products can be spray dried, vacuum dried or lyophilized.
  • the addition of 40 parts of the new compound I to this base with a general floral odor surprisingly brings about a significant modification of the odor in the direction of hyacinth.
  • the new, modified base has more character and radiance.
  • this base looks pleasantly flowery.
  • the new base is particularly suitable for soft, especially floral directions with a woody undertone. If you increase the concentration up to 2%, the wood note also comes more to the fore, it is expressed in a very nice sandal note, which is particularly evident in the background.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Fats And Perfumes (AREA)
  • Cosmetics (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Seasonings (AREA)

Description

Die Erfindung betrifft einen neuen Riech- und/oder Geschmackstoff. Es handelt sich dabei um die Verbindung der Formel

Figure imgb0001
also um das 2-Methyl-2-buten-1-yltiglat.The invention relates to a new fragrance and / or flavor. It is the compound of the formula
Figure imgb0001
 So the 2-methyl-2-buten-1-yltiglate.

Die Erfindung betrifft ferner ein Verfahren zur Herstellung der Verbindung der FormelThe invention further relates to a process for the preparation of the compound of the formula

Dieses Verfahren ist dadurch gekennzeichnet, dass man 2-Methyl-2-buten-1-o1 mit Tiglinsäure bzw. einem reaktiven Derivat davon verestert, dass man einen Tiglinsäureniederalkylester mit 2-Methyl-2-buten-1-ol umestert, oder dass man ein 2-Methyl-2-buten-1-yl-halogenid mit einem Alkalimetallsalz der Tiglinsäure umsetzt.This process is characterized in that 2-methyl-2-buten-1-o1 is esterified with tiglinic acid or a reactive derivative thereof, that one transesterifies a tiglinic acid lower alkyl ester with 2-methyl-2-buten-1-ol, or that a 2-methyl-2-buten-1-yl halide with an alkali metal salt of tiglinic acid.

Die Veresterung der Tiglinsäure bzw. deren Derivat kann nach an sich bekannten Methoden durchgeführt werden, also z.B. gemäss Tabelle I (siehe dazu auch "Organikum", Org. chem. Grundpraktikum, VEB Deutscher Verlag der Wissenschaften, Berlin 1969, 9. Auflage, S. 440 ff).

Figure imgb0002
The esterification of tiglinic acid or its derivative can be carried out according to methods known per se, for example according to Table I (see also "Organikum", Org. Chem. Grundpraktikum, VEB Deutscher Verlag der Wissenschaften, Berlin 1969, 9th edition, p . 440 ff).
Figure imgb0002

Bei der Umesterung wird als Tiglinsäure-niederalkylester insbesondere der Methyl- oder der Aethylester eingesetzt, da sich so die bei der Reaktion bildenden niedrig siedenden Alkohole Methanol bzw. Aethanol leicht abdestillieren lassen.In the transesterification, the tiglinic acid lower alkyl ester used is in particular the methyl or the ethyl ester, since the low-boiling alcohols formed in the reaction, methanol or ethanol, can thus be easily distilled off.

Die Verbindung I weist besondere organoleptische Eigenschaften auf, auf Grund derer sie sich vorzüglich als Riech- und/oder Geschmackstoff eignet.The compound I has special organoleptic properties, on the basis of which it is particularly suitable as a fragrance and / or flavoring.

Die Erfindung betrifft demgemäss auch die Verwendung der Verbindung I als Riech- und/oder Geschmackstoff.The invention accordingly also relates to the use of the compound I as a fragrance and / or flavoring.

Die erfindungsgemäss als Riech- und/oder Geschmackstoff verwendete Verbindung I zeichnet sich durch einen originellen und für einen Ester dieser Kohlenstoffzahl sehr überraschenden Geruch aus. Dieser kann wie folgt beschrieben werden: an feuchten Waldboden erinnernd, pilzartig (Champignon), leicht anisartig, blumig, weich, mit Aspekten des Geruches von jungen Blätterknospen. Auffallend ist das völlige Fehlen der fruchtigen Note und das Auftreten von als blumig zu klassierenden Nuancierungen und das Hervortreten des natürlichen Waldbodencharakters.The compound I used according to the invention as a fragrance and / or flavoring is distinguished by an original smell which is very surprising for an ester of this carbon number. This can be described as follows: reminiscent of damp forest soil, mushroom-like (mushroom), slightly anise-like, flowery, soft, with aspects of the smell of young leaf buds. What is striking is the complete absence of the fruity note and the appearance of nuances to be classified as floral and the emergence of the natural forest floor character.

Tiglate als Riechstoffe erfreuen sich in letzter Zeit zunehmender Beliebtheit. Unter ihnen finden sich aber keine Vertreter, die mit der erfindungsgemässen Verbindung organoleptisch vergleichbar wären.Tiglates as fragrances have recently become increasingly popular. However, there are no representatives among them who would be organoleptically comparable to the compound according to the invention.

S. Arctander beschreibt in "Perfume and Flavor Chemicals" (1969, Montclair NJ, USA) z.B. die folgenden strukturähnlichen Tiglate:

  • No. 1630:cis-3-Hexenyltiglat frisch, kräftig, tiefgrüne Blätter mit leicht fruchtigem Unterton
  • No. 1631 :trans-2-Hexenyltiglat warm-krautiger, grüner Geruch mit leicht fruchtigem Unterton
  • No. 1682:n-Hexyltiglat angenehmer süss-grüner, öliger, krautiger und leicht weinartiger Geruch, der an unreife Beeren oder Pflaumen erinnert
  • No. 225:iso-Amyltiglat angenehmer krautiger und weinartiger Geruch, an Medizinalkräuter erinnernd No. 540:n-Butyltiglat warm-krautig, diffusiv, ätherisch und süss.
In "Perfume and Flavor Chemicals" (1969, Montclair NJ, USA), S. Arctander describes, for example, the following structure-like tiglates:
  • No. 1630: cis-3-hexenyltiglate fresh, strong, deep green leaves with a slightly fruity undertone
  • No. 1631: trans-2-Hexenyltiglat warm-herbaceous, green smell with a slightly fruity undertone
  • No. 1682: n-Hexyltiglat pleasant sweet-green, oily, herbaceous and slightly wine-like smell, reminiscent of unripe berries or plums
  • No. 225: iso-amyltiglate pleasant herbaceous and wine-like smell, reminiscent of medicinal herbs No. 540: n-butyl tiglate warm-herbaceous, diffusive, ethereal and sweet.

Aber auch der olfaktische Vergleich mit dem 2-Methyl-2-buten-1-yl-2-methylbutyrat 2, dem 2-Methyl-butyltiglat 3 und dem als Insektenbekämpfungsmittel bekannten Prenylsenecioat 4 (CH-PS 2 64 520, 16.1.1950 und US―PS 2,554,947,29. Mai 1951) zeigt ausserdem, dass auch keine dieser Verbindungen die typischen olfaktischen Eigenheiten des 2-Methyl-2-buten-1-yltiglates I besitzt und nur gerade I die an feuchten Waldboden erinnernde, zugleich aber auch weich-blumige und knospenartige Geruchskombination ohne jeden fruchtigen Aspekt in ihrem Molekül vereint.

Figure imgb0003
But also the olfactory comparison with the 2-methyl-2-buten-1-yl-2-methylbutyrate 2, the 2-methyl-butyltiglate 3 and the prenylsenecioate 4 known as insecticide (CH-PS 2 64 520, 1 6.1.1950 and U.S. Patent No. 2,554,947,29. May 1 9 5 1) shows F urthermore, that none of these compounds typical olfaktischen characteristics of the 2-methyl-2-buten-1-yltiglates I has only just I reminiscent of moist soil , but at the same time also combined soft-flowery and bud-like combination of smells without any fruity aspect in their molecule.
Figure imgb0003

Geruchodor

estrig, fruchtig, beerenartig, Aspekte von schwarzem Holunder

Figure imgb0004
krautrig, süss mit grünem und leicht fruchtigem Unterton
Figure imgb0005
warm-krautig, grün, kerbelartigespresso, fruity, berry-like, aspects of black elder
Figure imgb0004
 herbaceous, sweet with a green and slightly fruity undertone
Figure imgb0005
 warm-herbaceous, green, chervil-like

Die Verbindung I kann demgemäss beispielsweise zur Parfümierung bzw. Aromatisierung von Produkten, wie Kosmetika (Seifen, Salben, Pudern, Zahnpasten, Mundwässern, Desodorantien, Shampoos, Lotionen, etc.), Detergentien, bzw. Nahrungsmitteln, Genussmitteln und Getränken dienen, wobei die Verbindung I vorzugsweise nicht allein, sondern in Form von Kompositionen mit andern Riech- bzw. Geschmackstoffen eingesetzt werden. Solche Riech- bzw. Geschmackstoffkompositionen mit einem Gehalt an I und deren auf an sich bekannte Art erfolgende Herstellung (Zugabe von I zu bekannten Riech- bzw. Geschmackstoffkompositionen oder Vermischung von I mit als Bestandteil von Riech- bzw. Geschmackstoffkompositionen geeigneten natürlichen oder synthetischen Verbindungen oder Gemischen) bildet ebenfalls Gegenstand der Erfindung.Accordingly, the compound I can be used, for example, for perfuming or aromatizing products, such as cosmetics (soaps, ointments, powders, toothpastes, mouthwashes, deodorants, shampoos, lotions, etc.), detergents, or foods, luxury foods and beverages, the Compound I is preferably not used alone, but in the form of compositions with other fragrances or flavors. Such fragrance or flavoring compositions with a content of I and their preparation in a manner known per se (addition of I to known fragrance or flavoring compositions or mixing of I with natural or synthetic compounds suitable as a component of fragrance or flavoring compositions or Mixtures) also form the subject of the invention.

Als Riechstoff eignet sich die Verbindung I auf Grund ihrer oben beschriebenen, originellen Noten, insbesondere in Kombination mit einer Reihe von natürlichen und synthetischen Riechstoffen wie z.B.

  • -Patchouliöl, Fichtennadel Absolue, Baummoos Absolue, Weihrauchbalsam, Sandelholzöl, Basilikumöl, Beifussöl, Kamillenöl, Salbeiöl, Tagetesöl, Ylang-Ylang-Oel, Bergamotteöl, Zitronenöl Petitgrainöl, Neroliöl, usw.
  • -Aldehyden wie Hydroxycitronellal, a-Hexylzimtaldehyd, Laurinaldehyd, Methylnonylacetaldehyd, 2,4-Dimethyl-3-cyclohexenyl-1-carboxaldehyd'(Cyclam®). Citral Cyclamenaldehyd; Anisaldehyd, usw.
  • -Ketonen wie α-Jonon, β-Jonon, Methyljonon, uww.
  • -Acetalen und Ketalen wie Phenylacetaldehyd-glycerinacetal (Acetal CD® (Givaudan)), 2-Methyl-13-dioxolan-2-äthylacetat (Fructon ®), usw.
  • -Aethern, wie Eukalyptol, Methyl-p-cresol, Anethol, Methyl-1-methylcyclododecyläther, usw.
  • -phenolischen Körpern wie Eugenol, Isoeugenol, usw.
  • -Alkoholen wie Linalool, Citronellol, Geraniol, Zimtalkohol, Benzylalkohol, Phenyläthylalkohol, a-Terpineol, usw.
  • -Estern wie Linalylacetat, Bornylacetat, Vetiverylacetat, Geranylacetat, Benzylacetat, Benzylsalicylat, Amylsalicylat, Styrallylacetat, Phenyläthylphenylacetat, Methyldihydrojasmonat, usw.
  • -Lactonen wie y-Nonalacton, y-Decalacton, y-Undecalacton, δ-Decalacton, usw.
  • -Säuren wie Phenylessigsäure, a-Methylbuttersäure, usw.
  • -moschus- und ambraartig riechenden Körpern wie Aethylenbrassylat, Keton-Moschus, 8α,12-Oxido-13,14,15,16-tetranorlabdan, usw.
  • -schwefelhaltigen Verbindungen wie p-Menthan-8-thiol-3-on, usw.
  • -stickstoffhaltigen Verbindungen wie Methylanthranilat, Linalylanthranilat, usw.
Compound I is suitable as a fragrance on the basis of its original notes described above, in particular in combination with a number of natural and synthetic fragrances such as, for example
  • Patchouli oil, spruce needle absolute, tree moss absolute, frankincense balm, sandalwood oil, basil oil, mugwort oil, chamomile oil, sage oil, tagetes oil, ylang-ylang oil, bergamot oil, lemon oil, petitgrain oil, neroli oil, etc.
  • Aldehydes such as hydroxycitronellal, a-hexylcinnamaldehyde, lauric aldehyde, methylnonylacetaldehyde, 2,4-dimethyl-3-cyclohexenyl-1-carboxaldehyde '(Cyclam®). Citral cyclamenaldehyde; Anisaldehyde, etc.
  • Ketones such as α-Jonon, β-Jonon, Methyljonon, etc.
  • Acetals and ketals such as phenylacetaldehyde glycerol acetal (Acetal CD® (Givaudan)), 2-methyl-13-dioxolane-2-ethyl acetate (Fructon®), etc.
  • -Ethers, such as eucalyptol, methyl-p-cresol, anethole, methyl-1-methylcyclododecyl ether, etc.
  • -phenolic bodies such as eugenol, isoeugenol, etc.
  • -Alcohols such as linalool, citronellol, geraniol, cinnamon alcohol, benzyl alcohol, phenylethyl alcohol, a-terpineol, etc.
  • -Esters such as linalyl acetate, bornyl acetate, vetiveryl acetate, geranyl acetate, benzyl acetate, benzyl salicylate, amyl salicylate, styrallyl acetate, phenylethylphenylacetate, methyldihydrojasmonate, etc.
  • Lactones such as y-nonalactone, y-decalactone, y-undecalactone, δ-decalactone, etc.
  • -Acids such as phenylacetic acid, a-methylbutyric acid, etc.
  • -musky and amber-smelling bodies such as ethylene brassylate, ketone musk, 8α, 12-oxido-13,14,15,16-tetranorlabdan, etc.
  • sulfur-containing compounds such as p-menthan-8-thiol-3-one, etc.
  • nitrogen-containing compounds such as methyl anthranilate, linalyl anthranilate, etc.

Wie aus den unten stehenden Beispielen 2-8 ersichtlich, lassen sich mit I sehr interessante Effekte erzielen. Neben wertvollen und originellen Effekten in Riechstoffkompositionen vom Typ Chypre, Cologne, Holz, Jasmin, Rose bzw. allgemein blumiger Richtung ist est aber auch möglich, mit dem 2-Methyl-2-buten-1-yltiglat neuartige Parfümerie-Komplexe herzustellen. So werden z.B. blumigfruchtige Komplexe aus Linalool und einem Lacton, wie z.B. 8-Decalacton durch Zusatz von 1-5% I harmonisiert und durch einen zusätzlichen exotischen Aspekt bereichert. kann auch bei der Rekonstitution von ätherischen Oelen oder Absolues verwendet werden.As can be seen from Examples 2-8 below, very interesting effects can be achieved with I. In addition to valuable and original effects in fragrance compositions of the type chypre, cologne, wood, jasmine, rose or generally floral, it is also possible to use the 2-methyl-2-buten-1-yltiglate to produce novel perfume complexes. For example, flowery fruit complexes of linalool and a lactone, such as 8-Decalactone harmonized by adding 1-5% I and enriched with an additional exotic aspect. can also be used in the reconstitution of essential oils or absolutes.

Bei der Herstellung solcher Kompositionen können die oben aufgeführten bekannten Riechstoffe nach (dem Parfumeur bekannter) Art und Weise verwendet werden, wie z.B. aus W. A. Poucher, Perfumes, Cosmetics and Soaps 2, 7. Auflage, Chapman und Hall, London, 1974 hervorgehend.In the preparation of such compositions, the known fragrances listed above can be used in a manner known to the perfumer, e.g. from W. A. Poucher, Perfumes, Cosmetics and Soaps 2, 7th edition, Chapman and Hall, London, 1974.

Die Konzentration der Verbindung 1 kann je nach dem Verwendungszweck innerhalb weiter Grenzen variieren, beispielsweise zwischen etwa 0,01 (Detergentien) und etwa 15 Gew.% (alkoholische Lösungen). In Parfumbasen bzw. Konzentraten können die Konzentrationen selbstverständlich auch höher liegen. Die Parfumbasen können in üblicher Weise zur Parfümierung von Eaux de Cologne, Eux de toilette, Extraits, Lotionen, Cremes, Shampoos, Seifen und Detergentien, etc. verwendet werden. Bevorzugt ist die Verwendung von I in Colognes und in Extraits.The concentration of compound 1 can vary within wide limits, depending on the intended use, for example between about 0.01 (detergents) and about 15% by weight (alcoholic solutions). The concentrations in perfume bases or concentrates can of course also be higher. The perfume bases can be used in the usual way for perfuming Eaux de Cologne, Eux de toilette, extraits, lotions, creams, shampoos, soaps and detergents, etc. The use of I in colognes and in extraits is preferred.

Als Geschmackstoff kann die Verbindung I beispielsweise zur Erzeugung bzw. Verbesserung, Verstärkung, Steigerung oder Modifizierung von verschiedenen Aromatypen verwendet werden, wie diese z.B. zur Aromatisierung von Nahrungsmitteln (Joghurt, Süsswaren etc.), Genussmitteln (Tee etc.) und Getränken (Limonaden etc.) eingesetzt werden. Insbesondere lassen sich interessante Effekte bei der Modifizierung von Erdbeer- oder Kräuterteearomen durch einen Zusatz von I erzielen; siehe Tabelle II.As a flavoring compound I can be used, for example, to produce or improve, enhance, increase or modify various types of aromatics, such as these e.g. for flavoring foods (yogurt, sweets etc.), luxury foods (tea etc.) and beverages (lemonades etc.). In particular, interesting effects in the modification of strawberry or herbal tea aromas can be achieved by adding I; see table II.

Die ausgeprägten geschmacklichen Qualitäten des Esters I ermöglichen die Verwendung in geringen Konzentrationen. Eine geeignete Dosierung umfasst beispielsweise den Bereich von 0.1 ppm-100 ppm, vorzugsweise von 1 ppm-20 ppm im Fertigprodukt, d.h. dem aromatisierten Nahrungsmittel, Genussmittel oder Getränk.The pronounced taste qualities of the ester I enable the use in low concentrations. A suitable dosage includes, for example, the range from 0.1 ppm-100 ppm, preferably from 1 ppm-20 ppm in the finished product, i.e. the flavored food, luxury food or drink.

In der folgenden Tabelle sind Effekte zusammengestellt, wie sie sich mit dem Ester I erzielen lassen.

Figure imgb0006
The following table summarizes effects that can be achieved with Ester I.
Figure imgb0006

Die Verbindung kann auf übliche Weise mit den für Geschmackstoffkompositionen verwendeten Bestandteilen vermischt bzw. solchen Aromen zugesetzt werden. Unter den erfindungsgemäss verwendeten Aromen werden Geschmackstoffkompositionen verstanden, die sich auf an sich bekannte Art verdünnen bzw. in essbaren Materialien verteilen lassen. Sie können nach an sich bekannten Methoden in die üblichen Gebrauchsformen, wie Lösungen, Pasten oder Pulver übergeführt werden. Die Produkte können sprühgetrocknet, vakuumgetrocknet oder lyophilisiert werden.The compound can be mixed in a conventional manner with the constituents used for flavoring compositions or added to such flavors. The aromas used according to the invention are understood to mean flavoring compositions which can be diluted in a manner known per se or distributed in edible materials. They can be converted into the usual forms of use, such as solutions, pastes or powders, using methods known per se. The products can be spray dried, vacuum dried or lyophilized.

Die bei der Herstellung solcher Aromen zweckmässigerweise verwendeten bekannten Aromastoffe sind entweder in der obigen Zusammenstellung bereits enthalten oder können leicht der Literatur entnommen werden, wie z.B. J. Merory, Food Flavorings, Composition, Manufacture and Use, Second Edition, The Avi Publishing Company, Inc., Westport, Conn. 1968, oder G. Fenaroli, Fenaroli's Handbook of Flavor Ingredients, Second Edition, Volume 2, CRC-Press, Inc. Cleveland, Ohio, 1975.The known flavoring substances expediently used in the production of such flavors are either already included in the above compilation or can easily be found in the literature, e.g. J. Merory, Food Flavors, Composition, Manufacture and Use, Second Edition, The Avi Publishing Company, Inc., Westport, Conn. 1968, or G. Fenaroli, Fenaroli's Handbook of Flavor Ingredients, Second Edition, Volume 2, CRC-Press, Inc. Cleveland, Ohio, 1975.

Für die Herstellung solcher üblicher Gebrauchsformen kommen beispielsweise folgende Trägermaterialien, Verdickungsmittel, Geschmackstoffverbesserer, Gewürze und Hilfsingredientien, etc. in Frage:

  • Gummi arabicum, Tragant, Salze oder Brauereihefe, Alginate, Carrageen oder ähnliche Absorbentien; Indole, Maltol, Gewürzoleoresine, Raucharomen; Gewürznelken, Natriumcitrat; Mononatriumglutamat, Dinatrium-inosin-5'-monophosphat (IMP), Dinatriumguanosin-5-phosphat (GMP); oder spezielle Aromastoffe, Wasser, Aethanol, Propylenglykol, Glycerin.
The following carrier materials, thickeners, flavor improvers, spices and auxiliary ingredients, etc. are suitable for the production of such customary forms of use:
  • Gum arabic, tragacanth, salts or brewer's yeast, alginates, carrageenan or similar absorbents; Indoles, maltol, spice oleoresins, smoke flavors; Cloves, sodium citrate; Monosodium glutamate, disodium inosine 5'-monophosphate (IMP), disodium guanosine 5-phosphate (GMP); or special flavors, water, ethanol, propylene glycol, glycerin.

Beispiel 1example 1

Zu einer Lösung von 106,2 g (1,24 Mol) 2-Methyl-2-buten-1-ol und 172,5 g (1,43 Mol) Dimethylanilin in 350 ml Toluol liess man im Verlaufe von 30 Minuten eine Lösung von 133,6 g (1,13 Mol) Tiglinsäurechlorid in 100 ml Toluol tropfen und rührte anschliessend das Reaktionsgemisch während 16 Stunden bei 40°, kühlte dann auf Raumtemperatur, verdünnte mit 200 ml Aether, wusch bis zur vollständigen Entfernung des überschüssigen Dimethylanilins mit verdünnter Salzsäure, hierauf mit Wasser bis zum Neutralpunkt. Nach dem Trocknen mit Natriumsulfat und Einengen verblieben 212 g rohes I, aus welchem durch Destillation über eine 20 cm-Widmerkolonne 131,5 g reines und olfaktisch gutes I vom Siedepunkt 92°/16.10-3 bar erhalten wurden.A solution was left over 30 minutes to a solution of 106.2 g (1.24 mol) of 2-methyl-2-buten-1-ol and 172.5 g (1.43 mol) of dimethylaniline in 350 ml of toluene drop of 133.6 g (1.13 mol) of tiglinic acid chloride in 100 ml of toluene and then the reaction mixture was stirred at 40 ° for 16 hours, then cooled to room temperature, diluted with 200 ml of ether, washed with dilute until the excess dimethylaniline had been completely removed Hydrochloric acid, then with water to neutral. After drying with sodium sulfate and concentration, 212 g of crude I remained, from which 131.5 g of pure and olfactically good I with a boiling point of 92 ° / 16.10 -3 bar were obtained by distillation over a 20 cm Widmer column.

Spektrale Daten:

  • IR: 1715, 1265, 1255, 1155, 1138, 1072, 732 cm-1
  • NMR: 1,6-1,9 (4 CH3 auf Doppelbindung, gegenseitig überlagert) 4,58
    Figure imgb0007
    Figure imgb0008
    ppm
  • MS: 168 (M+,2), 139(8), 123(8), 101(13), 83(100), 69(32), 55(55), 41(43), 39(23), 27(21)
Spectral data:
  • IR: 1715, 1265, 1255, 1155, 1138, 1072, 732 cm -1
  • NMR: 1.6-1.9 (4 CH 3 on double bond, mutually superimposed) 4.58
    Figure imgb0007
    Figure imgb0008
     ppm
  • MS: 168 (M +, 2), 139 (8), 123 (8), 101 (13), 83 (100), 69 (32), 55 (55), 41 (43), 39 (23), 27 (21)

Beispiel 2Example 2 Parfumerie-Base Richtung ChyprePerfume base towards Chypre

Figure imgb0009
Gibt man zu dieser konventionellen Chyprekomposition 20 Teile des neuen Esters, so erhält erstere eine viel frischere Kopfnote, das Bergamotteöl wird vorteilhaft unterstrichen, die ganze Base wirkt nun weicher und leichter.
Figure imgb0009
 If you add 20 parts of the new ester to this conventional chypre composition, you get the former a much fresher top note, the bergamot oil is advantageously underlined, the whole base now appears softer and lighter.

Beispiel 3Example 3 Blumige Base für die ParfumerieFlowery base for perfumery

Figure imgb0010
Gibt man zu dieser blumigen Base, welche Richtung Ylang neigt, 40 Teile des neuen Esters I, so wirkt erstere viel weicher, allgemein blumig und viel diffusiver. Dieser Effekt ist auch nach 24 Stunden noch sehr gut feststellbar.
Figure imgb0010
 If you add 40 parts of the new ester I to this floral base, which tends towards Ylang, the former looks much softer, generally floral and much more diffusive. This effect is still very noticeable after 24 hours.

Beispiel 4Example 4 Parfumerie-Base Richtung Eau de ColognePerfume base towards Eau de Cologne

Figure imgb0011
Gibt man zu diesem Eau de Cologne 6 Teile der neuen Substanz, so wirkt ersteres viel frischer, kräftiger, es entsteht eine sehr angenehm würzige Zitrusschalen-Note, welche in der ursprünglichen Base nicht vorhanden ist. Bei steigender Konzentration (1% und 2%) entsteht ein sehr origineller, herber Effekt, welcher der Komposition mehr Leben verleiht und sie insbesondere für Herren-Colognes sehr geeignet macht.
Figure imgb0011
 If you add 6 parts of the new substance to this eau de cologne, the former looks much fresher, stronger, and there is a very pleasantly spicy note of citrus peel, which is not present in the original base. With increasing concentration (1% and 2%) there is a very original, bitter effect, which gives the composition more life and makes it particularly suitable for men's colognes.

Beispiel 5Example 5 Parfumerie-Base allgemein-blumiger RichtungPerfumery base with a general floral direction

Figure imgb0012
Ein Zusatz von 40 Teilen der neuen Verbindung I zu dieser Base mit allgemein-blumigem Geruch bewirkt überraschenderweise eine deutliche Modifizierung des Geruches in Richtung Hyazinthe. Die neue, modifizierte Base besitzt mehr Charakter und Strahlungskraft.
Figure imgb0012
 The addition of 40 parts of the new compound I to this base with a general floral odor surprisingly brings about a significant modification of the odor in the direction of hyacinth. The new, modified base has more character and radiance.

Beispiel 6Example 6 Frisch-Grüne-Base für ParfümerieFresh green base for perfumery

Figure imgb0013
Gibt man zu dieser frisch-grünen Base 30 Teile der neuen Substanz, so wirkt erstere viel kräftiger, natürlicher. Es wird ein sehr angenehmer Waldduft festgestellt. Das Bornylacetat wird angenehm und deutlich hervorgehoben.
Figure imgb0013
 If you add 30 parts of the new substance to this fresh green base, the former looks much stronger, more natural. A very pleasant forest scent is found. The bornyl acetate is pleasantly and clearly emphasized.

Beispiel 7Example 7 Holzige Parfümerie-BaseWoody perfumery base

Figure imgb0014
Gibt man zu dieser Base (allgemein holzige Richtung) 0.5% der neuen Substanz, so wirkt erstere angenehm blumig untermalt; die neue Base eignet sich besonders für weiche, insbesondere blumige Richtungen mit holziger Unternote. Steigert man die Konzentration bis zu 2%, so tritt die Holz-Note ebenfalls mehr in den Vordergrund, sie äussert sich in einer sehr schönen Sandel-Note, die besonders in Fond hervortritt.
Figure imgb0014
 If 0.5% of the new substance is added to this base (generally woody direction), the former looks pleasantly flowery. the new base is particularly suitable for soft, especially floral directions with a woody undertone. If you increase the concentration up to 2%, the wood note also comes more to the fore, it is expressed in a very nice sandal note, which is particularly evident in the background.

Beispiel 8Example 8 KräuterteearomaHerbal tea aroma

Figure imgb0015
Der Zusatz von 50 Teilen 2-Methyl-2-butenyltiglat zu obigem konventionellen Kräuterteearoma bewirkt einen sehr angenehmen Abrundungseffekt, indem eine verstärkte blumige Note in Erscheinung tritt.
Figure imgb0015
 The addition of 50 parts of 2-methyl-2-butenyl tiglate to the above conventional herbal tea aroma brings about a very pleasant rounding-off effect, in that an intensified floral note appears.

Geschmacklich ist bei der Applikation von 50 g einer 2%-igen Lösung dieses Aromas in Glyceryltriacetat pro 100 I Zuckersirup 65° Bx (1 ° Brix = 1 Gew.% Rohrzucker), verdünnt mit Wasser im Verhältnis 1:5, ebenfalls eine deutliche Verbesserung feststellbar, indem nun im Gegensatz zur Blindprobe der Tee viel abgerundeter wirkt und zudem dank einer zusätzlichen blumigen Note an gewisse Schwarztee-Sorten erinnert.The taste when using 50 g of a 2% solution of this aroma in glyceryl triacetate per 100 l of sugar syrup 65 ° Bx (1 ° Brix = 1% by weight of cane sugar), diluted with water in a ratio of 1: 5, is also a significant improvement It can be determined that, in contrast to the blind sample, the tea now looks much more rounded and, thanks to an additional floral note, is reminiscent of certain types of black tea.

Claims (6)

1. 2-Methyl-2-buten-1-yl tiglate.
2. 2-Methyl-2-buten-1-yl tiglate as an odorant and/or flavourant.
3. Odorant and/or flavouring compositions characterized by a content of 2-methyl-2-buten-1-yl tigtate.
4. A process for the manufacture of 2-methyl-2-buten-1-yl tiglate, characterized in that one esterifies 2-methyl-2-buten-1-ol with tiglic acid or a reactive derivative thereof, or trans-esterifies a tiglic acid lower alkyl ester with 2-methyl-2-buten-1-ol, or reacts a 2-methyl-2-buten-1-yl halide with an alkali metal salt of tiglic acid.
5. A process for the perfuming of compositions or for the modification of the odour of odorant compositions, characterized in that one incorporates an organoleptically effective amount of 2-methyl-2-buten-1-yl tiglate in said compositions.
6. The use of 2-methyl-2-buten-1-yl tiglate as an odorant and/or flavourant.
EP79102139A 1978-06-28 1979-06-27 Tiglic acid ester, process for its preparation, its application and compositions containing it Expired EP0006616B1 (en)

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DE19939566C1 (en) * 1999-08-20 2001-04-05 Cognis Deutschland Gmbh Branched, largely unsaturated ester oils, process for their preparation and their use for the production of cosmetic and / or pharmaceutical preparations

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