GB2135302A - Substituted cyclohexenyl-ethanol derivatives and their use as smoke-flavour modifying agents - Google Patents

Substituted cyclohexenyl-ethanol derivatives and their use as smoke-flavour modifying agents Download PDF

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Publication number
GB2135302A
GB2135302A GB08401582A GB8401582A GB2135302A GB 2135302 A GB2135302 A GB 2135302A GB 08401582 A GB08401582 A GB 08401582A GB 8401582 A GB8401582 A GB 8401582A GB 2135302 A GB2135302 A GB 2135302A
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Prior art keywords
compound
smoke
ionone
flavour modifying
compounds
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GB08401582A
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GB8401582D0 (en
GB2135302B (en
Inventor
Adrian Gordon Barnes
Peter Charles Bevan
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British American Tobacco Investments Ltd
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British American Tobacco Co Ltd
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Priority claimed from GB838303406A external-priority patent/GB8303406D0/en
Application filed by British American Tobacco Co Ltd filed Critical British American Tobacco Co Ltd
Priority to GB08401582A priority Critical patent/GB2135302B/en
Publication of GB8401582D0 publication Critical patent/GB8401582D0/en
Publication of GB2135302A publication Critical patent/GB2135302A/en
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Publication of GB2135302B publication Critical patent/GB2135302B/en
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C35/00—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a ring other than a six-membered aromatic ring
    • C07C35/02—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a ring other than a six-membered aromatic ring monocyclic
    • C07C35/08—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a ring other than a six-membered aromatic ring monocyclic containing a six-membered rings
    • C07C35/18—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a ring other than a six-membered aromatic ring monocyclic containing a six-membered rings with unsaturation at least in the ring
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
    • A23L27/00—Spices; Flavouring agents or condiments; Artificial sweetening agents; Table salts; Dietetic salt substitutes; Preparation or treatment thereof
    • A23L27/20—Synthetic spices, flavouring agents or condiments
    • A23L27/203—Alicyclic compounds
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
    • A23L27/00—Spices; Flavouring agents or condiments; Artificial sweetening agents; Table salts; Dietetic salt substitutes; Preparation or treatment thereof
    • A23L27/20—Synthetic spices, flavouring agents or condiments
    • A23L27/24—Synthetic spices, flavouring agents or condiments prepared by fermentation
    • A—HUMAN NECESSITIES
    • A24—TOBACCO; CIGARS; CIGARETTES; SIMULATED SMOKING DEVICES; SMOKERS' REQUISITES
    • A24B—MANUFACTURE OR PREPARATION OF TOBACCO FOR SMOKING OR CHEWING; TOBACCO; SNUFF
    • A24B15/00—Chemical features or treatment of tobacco; Tobacco substitutes, e.g. in liquid form
    • A24B15/18—Treatment of tobacco products or tobacco substitutes
    • A24B15/20—Biochemical treatment
    • A—HUMAN NECESSITIES
    • A24—TOBACCO; CIGARS; CIGARETTES; SIMULATED SMOKING DEVICES; SMOKERS' REQUISITES
    • A24B—MANUFACTURE OR PREPARATION OF TOBACCO FOR SMOKING OR CHEWING; TOBACCO; SNUFF
    • A24B15/00—Chemical features or treatment of tobacco; Tobacco substitutes, e.g. in liquid form
    • A24B15/18—Treatment of tobacco products or tobacco substitutes
    • A24B15/28—Treatment of tobacco products or tobacco substitutes by chemical substances
    • A24B15/30—Treatment of tobacco products or tobacco substitutes by chemical substances by organic substances
    • A24B15/34—Treatment of tobacco products or tobacco substitutes by chemical substances by organic substances containing a carbocyclic ring other than a six-membered aromatic ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C33/00—Unsaturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
    • C07C33/05—Alcohols containing rings other than six-membered aromatic rings
    • C07C33/14—Alcohols containing rings other than six-membered aromatic rings containing six-membered rings
    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
    • C12P7/00—Preparation of oxygen-containing organic compounds
    • C12P7/02—Preparation of oxygen-containing organic compounds containing a hydroxy group

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Health & Medical Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Food Science & Technology (AREA)
  • Zoology (AREA)
  • Biochemistry (AREA)
  • Polymers & Plastics (AREA)
  • Nutrition Science (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Biotechnology (AREA)
  • Bioinformatics & Cheminformatics (AREA)
  • General Engineering & Computer Science (AREA)
  • Microbiology (AREA)
  • Genetics & Genomics (AREA)
  • Toxicology (AREA)
  • Manufacture Of Tobacco Products (AREA)
  • Preparation Of Compounds By Using Micro-Organisms (AREA)

Abstract

In a method for the production of a smoke-flavour modifying agent, beta ionone is contacted with a fungal culture to effect transformation of at least a proportion of the beta -ionone to a product comprising at least one compound of the group consisting of Compound A, Compound B and Compound C, of formulae <IMAGE> The invention also includes the smoke-flavour modifying agent so produced and/or smoking a material or article comprising the said agent or smoking article produced.

Description

SPECIFICATION Improvements relating to smoke-flavour modifying agents This invention relates to smoke-flavour modifying agents and a method of production thereof.
Flavour-modifying agents provide an additional tool for the assistance of the tobacco blender whereby control for the attainment of a desired smoke-flavour can be excercised more reliably and/or with greater economy.
ssionone is a compound used in perfumery.
Its full chemical name is: 4-(2,6,6-trimethyl-1- cyclohexen-1-yl)3-buten-2-one and it is available in commerce. As used in the present invention, it was obtained from Aldrich Chemical Company of Milwaukee, Wisconsin 53233, U.S.A. as a liquid of 98% purity and boiling point of 126-1 28'C.
According to the present invention there is provided a method for the production of a smoke-flavour modifying agent, wherein ss- ionone is contacted with a fungal culture to effect a transformation of at least a proportion of the P-ionone to a product comprising at least one compound of the group consisting of a Compound A, Compound B and Compound C, each of which compounds is a respectively defined (hereinbelow).
Also according to the invention, a smokeflavour modifying agent for incorporation with a smoking material comprises one or more compounds from the group consisting of the said Compound B and the said Compound C.
A product comprising Compounds A, B and C may be used as a tobacco-smoke flavourmodifying agent. Alternatively, one or more of the compounds, advantageously being or including the higher-yielding Compound A may be first extracted and the extracted compound or compounds used as tobacco-smoke flavour modifying agent or agents.
The smoking material may be tobacco, a reconstituted tobacco material or a tobacco substitute material. The agent may be incorporated with a smoking material by being sprayed thereon in a volatile solvent. The agent is suitably added to the smoking material at a loading level within a range of 5 to 2,000 parts per million of smoking material, but preferably in a range of 100 to 500 parts per million.
The chemical structure of Compound A, which is a compound known per se, may be represented as:
The chemical structure of Compound B may be represented as:
The chemical structure of Compound C may be represented as:
We have discovered that a wide range of fungi may be used in the transformation of ss- ionone to products comprising 2,6,6-trime thyl-1-cyclohexene-1-ethanol (Compound A), 4-hydroxy-2,6,6-trimethyl-1 -cyclohexene-1 - ethanol (Compound B) and 2-hydroxymethyl6, 6-dimethyl-1 -cyclohexene- 1-ethanol (Compound C).Of twenty-seven fungal shake-flask cultures it was found that eleven were effective in transforming p-ionone to give Compound A, although considerable variations in extent of conversion were found. With five of the eleven fungi, Compound B and Compound C were also found to be present. The eleven fungi were identified as species of Aspergillus (3 strains), Penicillium (1 strain), Cladosporium (1 strain), Ophiobolus (1 strain), Abortiporus (1 strain), Beauveria (1 strain), Yeast (1 strain) and Phoma (1 strain). One could not be identified due to lack of sporulation. Examples of suitable fungi are: Cladosporium oxysporum (CBS 548.80) Abortiporus ciennis (CBS 365.74) Beauveria bassiana (CBS 209.27) Ophiobolus herpotrichus (CBS 240.31) All four of the above named fungi are obtainable from the Centraalbureau Voor Schimmelcultures, Oosterstraat 1, Baarn, Holland.The culture deposit having the accession number CBS 548.80 was made with the Centraalbureau Voor Schimmelcultures on 25th May, 1 980 and characteristics of it are given in United Kingdom Patent Specification No. 2,093,446A, to which reference is directed.
The selection of micro-organisms which possess the property of transforming fi-ionone to yield Compounds A, B or C was made by incubating fi-ionone with a range of microorganisms obtained from culture collections and by direct isolation from natural substances such as soil and tobacco leaves. The novel compounds were identified by comparing extracts from the culture media with controls comprising culture media having no ionone. The compounds were then isolated and purified and predetermined proportions thereof were incorporated with cigarette tobacco.
Cigarettes filled with this tobacco were smoked by an expert panel of smokers to assess the effect of the respective products on the tobacco smoke. In all cases, smokers noted an appreciable effect upon the flavour of the smoke, but without the intrusion of any undesirable smoke attribute.
The following examples illustrate procedures for obtaining the p-ionone compounds and the nature of the products obtained: Example 1 A pure culture of Cladosporium oxysporum CBS 548.80 was inoculated into two 250 ml Erlenmeyer flasks each containing 100 ml sterile malt extract broth of formula:: Malt extract 1 7 g Mycological peptone 3 9 Distilled water 1000 ml pH 5.4 The flasks were incubated on an orbital shaker at room temperature, with a shaker speed of 1 50 rpm, for four days in order to obtain a growth of C. oxysporum. 100 mg of fl-ionone, dissolved in polyoxyethylene sorbitan monooleate, supplied by Sigma Chemicals, Poole, England, under the trade name ''Tween 80", was then added to one of the two flasks and in equal quantity to a third flask containing 100 ml of the sterile malt extract, but no fungus.Incubation of all three flasks was continued for a further seven days after which the content of each flask was extracted with 1,1,1 -trichloroethane. After concentration, the extracted products from the three flasks were compared with each other by means of thin layer chromatography (TLC), using silica gel plates and a 9:1 chloroform/ methanol solvent. For visualisation purposes, the plates were sprayed with a mixture of anisaldehyde and sulphuric acid and then heated. In the case of the product from the flask in which fi-ionone was added to the fungus culture, the TLC procedure indicated the presence of three substances additional to fl-ionone. These substances were not present in the extracts from the other two flasks.It was thus concluded that the three additional substances had resulted from a transformation of the p-ionone brought about by the C.
oxysporum fungus. The three additional substances produced were all more polar than ss- ionone by Rf value in the TLC system: Substance I Rf 0.41 Substance II Rf 0.12 Substance Ill Rf 0.11 p-ionone Rf 0.64 Substances I, II and Ill were separated by a combination of column, high pressure liquid and thin layer chromatography and each was then identified using gas chromatographymass spectrometry, nuclear magnetic resonance and infra-red analysis.The following identities were established:: Substance I 2,6,6-trimethyl-1 -cyclohexene- ethanol Substance II 4-hydroxy-2,6,6-trimethyl-1- cyclohexene- 1 -ethanol Substance Ill 2-hydroxymethyl-6, 6-dimethyl 1 -cyclohexene- 1-ethanol Thus Substance I is Compound A, Substance II is Compound B and Substance Ill is Compound C.
Example 2 The procedure of Example 1 was followed except that the broth was of the following formula: Sucrose 3 9 MgSO4 0.05 g K2HPO4 0.2 g NaNO3 0.2 g KH2PO4 0.1 g Cornsteep liquor 1.0 g At the conclusion of incubation, the presence of Compounds A, B and C was demonstrated.
Example 3 As Example 1, but using a broth of the following formula: Sucrose 5.0 g MgSO4 0.05 g K2HPO4 0.1 g NaNO3 0.2 g KCI 0.05 g Yeast Extract 0.1 g At the conclusion of incubation, the presence of Compounds A, B and C was demonstrated.
Example 4 2.5 1 of sterile malt extract broth in a 3 fermenter vessel was inoculated with C. oxysporum and incubated at 28"C with continuous stirring and aeration. After 24 hours, 2.5 mls of fi-ionone dissolved in Tween 80 was added. The incubation was then continued for a further 1 60 hours, with samples taken at daily intervals. Analysis of these samples showed the p-ionone gradually disappeared over the continuation incubation period and that Compounds A, B and C gradually appeared.
Example 5 The general procedure of Example 4 was followed but a 20 1 vessel containing 10 1 of sterile malt extract broth was used. 10 mls of ssionone in 40 mls of Tween 80 was added and the broth stirred at 400 rpm and aerated at 6.0 I/min. 3.29 gms of mixed products containing compounds identified as A, B and C were extracted from the broth after 1 60 hours incubation. The relative yields were, Compound A 330 mg; Compound B 220 mg; and Compound C 40 mg.
Example 6 As Example 1, but using a pure culture of Abortiporus ciennis CBS 365.74 in place of C. oxysporum. At the conclusion of the seven day incubation period the Compounds A, B and C were found to be present.
Example 7 As Example 1, but using a pure culture of Beauveria bassiana CBS 209.27 instead of C.
oxysporum. At the conclusion of the seven day incubation period the Compounds A, B and C were found to be present.
Example 8 As example 1, but using a pure culture of Ophiobolus herpotrichus CBS 240.31 instead of C. oxysporum. At the conclusion of the seven days incubation period the Compounds A, B and C were found to be present.
For the purpose of assessing the smokemodifying properties of each of the Compounds A, B and C, an assessment panel smoked cigarettes having a filler of flue cured tobacco and cigarettes having American-style blended tobacco fillers to each of which one of the Compounds A-C had been added. The effect of each compound on the tobacco smoke was assessed against control cigarettes containing no added smoke-modifying agent.
Each of the cigarettes was of 9 mg total particulate matter delivery. The Compounds A-C were each added to the test cigarettes, by syringe, in the form of a solution in ethanol, the resultant loading level being 200 ppm for Compound A and 500 ppm for Compound B and Compound C. The control cigarettes had introduced into them the same quantity of ethanol but with nothing dissolved therein. Both the test and the control cigarettes were put aside for 48 hours before being smoked by the panel.
The properties of the compounds were determined to be as follows.
Compound A on Flue Cured Tobacco Smoothing and rounding with floral effects.
Compound A on Blended Tobacco Smoothing with sweet nutty notes.
Compound B on Flue Cured Tobacco Intense and tobacco-compatible with sweet high-pitched fruity green and woody notes.
Also adds body.
Compound B on Blended Tobacco Sweet notes and added body.
Compound C on Flue Cured Tobacco Enhanced overall tobacco flavour with floral Virginia notes.
Compound C on Blended Tobacco Green spicy grassy musty notes and smoothing effect.

Claims (9)

1. A method for the production of a smoke-flavour modifying agent, wherein ss- ionone is contacted with a fungal culture to effect a transformation of at least a proportion of the fi-ionone to a product comprising at least one compound of the group consisting of Compound A, Compound B and Compound C, each of which compounds is as respectively defined hereinabove.
2. A method according to Claim 1, wherein Compound A is extracted from the said product for incorporation with the smoking material.
3. A smoke-flavour modifying agent produced by the method of Claim 1 or 2.
4. A smoke-flavour modifying agent comprising at least one compound of the group consisting of Compound B and Compound C.
5. A smoking material comprising a smoke-flavour modifying agent according to Claim 3 or 4.
6. A smoking material as claimed in Claim 5, wherein the loading level of said agent is within a range of 5 to 2,000 parts per million of the smoking material.
7. A smoking material as claimed in Claim 6, wherein said loading level is within a range of 100 to 500 parts per million.
8. A smoking' article comprising smoking material according to any one of claims 5 to 7.
9. A method for the production of a smoke-flavour modifying agent, substantially as hereinbefore described in any one of examples 1 to 8.
GB08401582A 1983-02-08 1984-01-20 Substituted cyclohexenyl-ethanol derivatives and their use as smoke-flavour modifying agents Expired GB2135302B (en)

Priority Applications (1)

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GB08401582A GB2135302B (en) 1983-02-08 1984-01-20 Substituted cyclohexenyl-ethanol derivatives and their use as smoke-flavour modifying agents

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB838303406A GB8303406D0 (en) 1983-02-08 1983-02-08 Smoke-flavouring agents
GB08401582A GB2135302B (en) 1983-02-08 1984-01-20 Substituted cyclohexenyl-ethanol derivatives and their use as smoke-flavour modifying agents

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GB2135302A true GB2135302A (en) 1984-08-30
GB2135302B GB2135302B (en) 1986-07-16

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2017521493A (en) * 2014-07-02 2017-08-03 フイルメニツヒ ソシエテ アノニムＦｉｒｍｅｎｉｃｈ Ｓａ Prince reaction in hindered substrates

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2017521493A (en) * 2014-07-02 2017-08-03 フイルメニツヒ ソシエテ アノニムＦｉｒｍｅｎｉｃｈ Ｓａ Prince reaction in hindered substrates

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GB8401582D0 (en) 1984-02-22
GB2135302B (en) 1986-07-16

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