Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
  • C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
  • C07C45/30—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with halogen containing compounds, e.g. hypohalogenation
• • 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
  • A23L27/202—Aliphatic compounds
  • A23L27/2024—Aliphatic compounds having oxygen as the only hetero atom
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
  • C07C45/51—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition
  • C07C45/511—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition involving transformation of singly bound oxygen functional groups to >C = O groups
  • C07C45/515—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition involving transformation of singly bound oxygen functional groups to >C = O groups the singly bound functional group being an acetalised, ketalised hemi-acetalised, or hemi-ketalised hydroxyl group

Definitions

• This invention relates to the treatment of foodstuffs, more particularly to the treatment of foodstuffs to impart to them an improved savoury flavour.
• the invention depends on our discovery that an improved savoury flavour can be imparted to a foodstuff, or such savoury flavour as it already has can be enhanced or modified, by incorporating in the foodstuff a small proportion of an aliphatic aldehyde having from 11 to 17 carbon atoms and from 2 to 4 olefinic bonds, for example:
• precursors which can form the aldehydes (RCHO) by oxidation are the corresponding alcohols (RCH OH); and examples of precursors Which can form the aldehydes by hydrolysis are the corresponding acetals such as the diethyl acetals hemiacetals, and the esters (such as the acetates and propionates) of the hypothetical diols [RCH(OH corresponding to the aldehydes.
• a preferred precursor of this kind is arachidonic acid
• Examples of compounds in which n equals 3 are octadeca- 6,9,12-trienoic, nonadeca 7,10,13 trienoic and eicosa-8,- 11,14-trienoic acids.
• the C acid can be isolated by known methods from the seeds of the genus Oenothera, particularly the species 0. lamarckiana and 0. fruticosa; and the C and C acids can be derived from the C acid by chain-lengthening according to the well known Arndt-Eistert reaction. For flavouring it is preferred to employ all the above acids in the all-cis configuration.
• the precursor may itself be incorporated into the foodstuff, or it may be treated to yield the actual flavouring compound which, after purification or other treatment Which may be required, can then be added to the foodstuff.
• flavouring compound or its precursor is distributed over the surface of the foodstuff, for instance, by dipping, sprinkling or spraying.
• Examples of methods which may be employed in the preparation of the active flavouring compound from the precursor are set out later in the specification, but a preferred way of obtaining the active compound from a precursor involves oxidation of the precursor in the presence of a suitable catalyst and molecular oxygen.
• a particularly valuable catalyst for this purpose is chlorophyll, by use of which the time required for oxidation of a precursor is commonly reduced by a factor of ten or more compared with the time required for oxidation in the absence of such a catalyst.
• a particularly preferred method of obtaining the flavouring compound from the precursor involves autoxidation or oxidation of a percursor, followed by treatment with the bisulphite of an alkali metal, for example, sodium bisulphite.
• the oxidised precursor is shaken with a solution of the bisulphite, after which the flavouring compound is separated by distillation or solvent extraction.
• the precursor is submitted to oxidation in the presence of chlorophyll, after which a solution of sodium bisulphite is added to the oxidation product and the mixture distilled, preferably by steam distillation.
• a suitable amount of gaseous sulphur dioxide may be passed through the solution of the precursor either simultaneously with or subsequent to its oxidation.
• flavouring compound may be synthesised from a simpler substance.
• a particularly successful synthetic sequence is one in which is formed, as an intermediate compound, 2,5-hexadiynal,
• 2,5-hexadiyna'l is a novel compound, as are its acetals and hemiacetals, and its use is not limited to the preparation only of the aldehydes mentioned; indeed, by selection of suitable reactants and reaction conditions these compounds may be employed in the synthesis of a wide range of long chain unsaturated carbonyl compounds in addition to those specified above.
• the aldehydes are new compounds; as also are many of their precursors, particularly those capable of forming the aldehydes by oxidation or hydrolysis.
• the invention accordingly includes the aldehydes and those precursors that are new compounds, methods of preparing these compounds as described later and the new compounds synthesised en route.
• the invention also includes the use of the aldehydes and their precursors generally in flavouring food products, and the food products thus flavoured.
• the amount of the aldehyde used in flavouring a foodstuff is generally about 1 part in -40 parts of food product and preferably 1 part in 10 to 10 parts, but proportions outside this range can be employed in some circumstances.
• a precursor is added to the foodstuff it is preferably used in an amount sufficient to provide a quantity of the aldehyde with the range specified.
• flavouring compound or precursor Since only a very small proportion of the flavouring compound or precursor is usually required it is often convenient to use it in conjunction with a suitable diluent, for example an inert solvent, such as a bland fat or oil, certain hydrocarbons, water and esters of higher fatty acids such as are used as solvents in the pharmaceutical industry.
• a suitable diluent for example an inert solvent, such as a bland fat or oil, certain hydrocarbons, water and esters of higher fatty acids such as are used as solvents in the pharmaceutical industry.
• flavouring compound or precursor may also be used in conjunction with normally used fiavouring substances, so that the invention includes also flavouring compositions comprising the fiavouring compound of the invention, or a precursor thereof, and another flavouring substance.
• an improved savoury flavour may not develop immediately on the incorporation of the compound in the foodstuff; it will, however, usually develop within a few minutes of heating the product, or within a few hours of the product being allowed to stand in air at room temperature.
• the invention is particularly applicable to the preparation of foodstuffs having an improved flavour of chicken. It can, for example, be employed to improve the natural flavour of chicken meat.
• EXAMPLE 1 (Preparation of undeca-trans-Z, cis-S-dienal) Hept-l-yne (B.P. 102 C., n 1.4082) prepared in 50% yield from sodium acetylide and amyl bromide, was treated, in the form of its Grignard derivative, with propargyl bromide in the presence of cuprous chloride as catalyst.
• 1,1-diethoxyundeca-2,5-diyne was hydrogenated over Lindlars catalyst (lead-poisoned palladium), and the product, containing 1,1-diethoxyundeca-2,S-diene, was hydrolysed with tartaric acid at 100.
• the product contained 55% undeca-trans-Z, cis-S-dienal. [Dinitrophenylhydrazonez M.P. 113114; light absorption in chloroform, maximum 3780 A.]
• 1,1-diethoxyprop-2-yne (propargyl aldehyde diethyl acetal) was prepared by dehydrobromination with sodamide in liquid ammonia in about 70% yield, B.P. 40-43/11 mm.; 12 1.4118.
• 1,1-diethoxyprop-2-yne as its Grignard derivative, reacted with propargyl bromide in tetrahydrofuran with cuprous chloride as catalyst, to give 1,1-diethoxyhexa-2,5- diyne in 65% yield.
• 0 1-1 0 requires: 77.10% C; 11.50% H; 32.15% OC H I number 271.5.
• 1,1-diethoxytetradeca2,5,8-triene was hydrolysed with boiling 1% oxalic acid solution to give a mobile yellow oil, B.P. 9l%/0.05 mm., containing the parent triene aldehyde.
• the dinitrophenylhydrazone (orange-yellow needles) had an M.P. of 93.5-94".
• the l.l-diethoxyheptadeca-2,5,8,l'l-tetraene was hydrolysed with boiling 1% oxalic acid solution to give a product containing the parent tetraene aldehyde.
• the 2-methyltetradeca-5,8-diyne-2-ene was then treated with perbenzoic acid (obtained from benzoyl chloride and sodium peroxide) for 1 hour, the epoxy compound so formed decomposed and the diol obtained extracted with ether and dried over magnesium sulphate. Further purification of the diol was by chromatography on an alumina (deactivated with 8% water) column, with elution with 100% ether.
• the diol so obtained was next hydrogenated over Lindlars catalyst, giving methyltetradeca-S,8-diene-2,3- diol (n 1.4788), and this was then treated with sodium iodate in HgO/T-H-F. solution.
• the aldehyde was extracted with ether, dried over magnesium sulphate and the ether evaporated.
• EXAMPLE 6 This example illustrates the preparation of a flavouring agent according to the invention employing arachidonic acid as precursor.
• Example 6 was repeated using 'y-linolenic acid instead of arachidonic acid.
• the product obtained had a very similar flavour to that obtained from arachidonic acid.
• EXAMPLE 8 To a very dilute solution of sulphuric acid (3 drops of 2 N acid in 70 ml. of water) was added 1 gm. of arachidonic acid. This mixture was heated to boiling, and oxygen was bubbled through it with the simultaneous dropwise addition of a 25% solution of sodium bisulphite in water. The rate of addition was adjusted to maintain the volume of the mixture constant. The distillate was collected and, after removal of most of the sulphur dioxide on a rotary evaporator, was added to chicken 6 soup in an amount forming 0.1 ml. per 500 ml. of soup. The chicken flavour of the soup was improved very noticeably.
• EXAMPLE 9 The process described in Example 8 was repeated, except that instead of adding a solution of sodium bisulphite to the reaction mixture a stream of sulphur dioxide was blown through it, together with the stream of oxygen. Again, the distillate obtained imparted a very good chicken flavour to a soup base.
• EXAMPLE 10 A mixture of steam, sulphur dioxide and oxygen was passed through a sloping glass tube arranged so that the gases entered at the higher end and, after leaving the tube, passed immediately into a condenser. The tube was heated and ethyl arachidonate was allowed to fall, drop by drop, into it. The products of the reaction between the sulphur dioxide, oxygen and the ester were carried through the tube and condensed to give a condensate with a noticeable savoury (chicken-like) flavour.
• EXAMPLE 11 This example illustrates that oxidation of arachidonic acid is an essential step in the formation from it of the flavouring agent of the invention.
• Example 8 The process of Example 8 was repeated, except that the water used was carefully boiled to remove dissolved oxygen, and instead of oxygen a stream of nitrogen was bubbled through the reaction mixture.
• the distillate collected had only a very slight taste of chicken, which was probably produced by antoxidation of the arachidonic acid prior to the rteatment described above.
• EXAMPLE 12 The process described in Example 8 was repeated but using the ethyl ester of 'y-linoleic acid instead of arachigonic acid.
• the distillate obtained had a strong chicken avour.
• EXAMPLE 13 The process described in Example 8 was repeated, using the ethyl ester of nonadeca-7,10,l3-trienoic acid instead of arachidonic acid. Again, a distillate having a strong chicken flavour was obtained.
• EXAMPLE 14 This example illustrates the accelerated oxidation of methyl 'y-linolenate in the presence of chlorophyll.
• the apparatus used consisted of a glass tube 30 cm. long and 2.5 cm. in diameter, one end of the glass tube being constricted to take rubber tubing. Inside the glass tube, immediately adjacent the constriction and sealed to the sides of the glass tube, was arranged a transverse sintered glass disc. The whole length of the glass tube was jacketed so that water could be passed around it to maintain the inside of the glass tube at a desired temperature.
• the tube was arranged vertically with the sintered disc and constricted region at the bottom.
• the tube was irradiated by two 250 watt infrared lamps and the chlorophyll/hexane solution added to the ester at the rate of 0.01 ml. every 5 minutes. Reaction was allowed to continue for three hours, after which the tube was emptied and its contents taken up in carbon tetrachloride. The carbon tetrachloride solution was then shaken for 24 hours with a solution of ferrous ammonium sulphate, separated, and any organic material remaining in the ferrous ammonium sulphate extracted in fresh carbon tetrachloride. High vacuum distillation of the combined carbon tetrachloride solutions gave a fraction (B.P. 90-110" C./3 l0 mm.) having a very strong, clean chicken flavour.
• EXAMPLE Ethyl arachidonate (83% pure) in hexane solution was passed through a chromatographic column packed with deactivated alumina to remove most of the added antioxidant (propyl gallate) and the ester was then treated as described in the previous example.
• EXAMPLE 16 1 ml. of ethyl arachidonate, which had been oxidised as described in Example 14 to the point where the ester was removed from the tube after irradiation, was steam distilled with 75 ml. of a 50% aqueous solution of sodium bisulphite, and the distillate collected.
• the distillate had a good chicken flavour.
• Example 17 The process of Example 16 was repeated, except that 2 ml. of 2 N sulphuric acid were added to the oxidised ester before distillation was commenced. The distillate obtained had a very good chicken flavour.
• EXAMPLE 18 The processes described in Examples 16 and 17 were repeated, using oxidised arachidonic acid instead of ethyl arachidonate.
• the distillate in each case had substantially the same flavour as when the ester was treated.
• EXAMPLE l9 1 gm. of 'y-linolenic acid, oxidised as described in Example 14, was heated in a flask with 75 ml. of distilled water. During the heating a continuous stream of sulphur dioxide was bubbled through the mixture in the flask. The distillate was collected and was found to have a strong chicken flavour very similar to that obtained by the processes described in Examples 14 to 18.
• EXAMPLE 20 This example illustrates how, according to the invention, a soup having only a weak flavour of chicken, resulting from the presence in it of chicken meat and chicken fat, can be given a more marked chicken flavour by the incorporation of arachidonic acid.
• a conventional dry soup mixture was prepared by mixing together the following ingredients:
• the mixture was then simmered in 800 cc. of water for 7 minutes, and soup having a weak flavour of chicken resulted.
• a second dry soup mixture was then prepared, identical with the first except that the chicken fat employed was first mixed with 0.18 cc. of ethanol containing 10% by weight of commercially available (about 90% pure) arachidonic acid. The mixture was then simmered in 800 cc. of water for 7 minutes, to give a soup of excellent chicken flavour. It contained about 1 part of arachidonic acid per 50,000 parts of soup.
• EXAMPLE 22 Tetradeca-2,5,8-trienal obtained as described in Example 3 was diluted tenfold with ethanol and then 0.025 ml. of this diluted solution added to 850 cc. of neutral soup base. A very distinct mushroom flavour was apparent in the soup.
• EXAMPLE 23 (Preparation of tetradeca-trans-Z, cis-4, cis-S-trienal) 22.2 g. undeca-LSdiyne and 2.0 g. cuprous chloride, in 200 ml. aqueous methylamine were stirred vigorously while 78.0 g. of 1,1 diethoxy-3-bromo-prop-2-yne was added dropwise in thirty minutes. The colour of the solution was maintained by the addition of small amounts of hydroxylamine hydrochloride as required. The mixture was cooled and extracted with ether and the ether extract washed with ammonium chloride solution and then water. The ether extract was then dried over magnesium sulphate and freed of solvent in vacuo.
• Example 20 was repeated, except that instead of arachidonic acid, aldehydes prepared as described in Examples 1, 3, 4, 5 and 23 were incorporated into the soup.
• EXAMPLE 25 (Preparation of tetradeca-trans-Z, trans-4, cis-8-trienal)
• the DNPH of the product obtained in Example 23 was converted to the trans-2, trans-4, cis-8 compound by acidification with 2 N hydrochloric acid.
• a method of flavouring a foodstuff which comprises the step of incorporating in the foodstuff an aliphatic aldehyde or a precursor thereof, said aldehyde having the general formula RCHO Where R contains from 10 to 16 carbon atoms and from 2 to 4 double bonds with at least one of the double bonds being non-conjugated to a level such that the foodstuff contains one part of the aldehyde in about 10 to about 10 parts of the foodstuff.
• aldehyde is selected from the group consisting of undeca-2,5- dienal, dodeca-3,6-dienal, trideca-4,7-dienal, trideca-2,4,7- trienal, tetradeca-2,5,8-trienal, tetradeca-2,4,8-trienal, pentadeca-3,6,9-trienal, hexadeca-4,7,10-trienal, hexadeca-2,4, 7,10-tetraenal, and heptadeca-2,5,8,1l-tetraenal.
• a method according to claim 1 which comprises the steps of:
• a method according to claim 1 which comprises the steps of:
• a method according to claim 1 which comprises the steps of:
• a foodstuff having incorporated in it an aliphatic aldehyde of the general formula RCHO where R contains from to 16 carbon atoms and from 2 to 4 double bonds with at least one of the double bonds being non-conjugated, the amount of said aldehyde in the foodstuff being one part in about 10 to about 10 parts of the foodstuff to impart an enhanced flavour to the foodstuff.
• a fiavouring composition for use with foodstuffs which comprises an ester selected from the group consisting of an acetate of the formula RCH(CH COO) and a propionate of the formula RCH(C H COO) corresponding to an unsubstituted, straight-chained aliphatic aldehyde having the formula RCHO, where R is a residue having from 10 to 16 carbon atoms and 2 to 4 double bonds with at least one of the double bonds being non-conjugated, said ester being hydrolysable to said aldehyde.
• a fiavouring composition for use with foodstuffs which composition comprises a derivative selected from the group consisting of an acetal, a hemi-acetal and a bisulfite addition compound of an unsubstituted, straight chained aliphatic aldehyde having the formula RCHO, where R is a residue having 10 to 16 carbon atoms and 2 to 4 double bonds with at least one of the double bonds being non-conjugated, said derivative being hydrolysable to said aldehyde.
• a fiavouring composition for use with foodstuffs which composition comprises an alcohol of the general formula RCHOH, said alcohol being oxidisable to an unsubstituted, straight-chained aliphatic aldehyde of the formula RCHO, where R is a residue having 10 to 16 carbon atoms and 2 to 4 double bonds, at least one of the double bonds being non-conjugated.
• a fiavouring composition for use with foodstuifs which composition comprises an aliphatic aldehyde of the general formula RCHO, where R contains from 10 to 16 carbon atoms and from 2 to 4 double bonds, at least one of the double bonds being non-conjugated.

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• Chemical & Material Sciences (AREA)
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• Life Sciences & Earth Sciences (AREA)
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• Food Science & Technology (AREA)
• Polymers & Plastics (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

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Cited By (10)

• 1963
  • 1963-08-20 LU LU44297D patent/LU44297A1/xx unknown
  • 1963-08-21 NL NL63296925A patent/NL139102B/nl not_active IP Right Cessation
  • 1963-08-21 DK DK400363AA patent/DK112420B/da unknown
  • 1963-08-22 DE DE1517129A patent/DE1517129C3/de not_active Expired
  • 1963-08-23 IT IT17488/63A patent/IT1061785B/it active
  • 1963-08-23 SE SE9224/63A patent/SE316359B/xx unknown
  • 1963-08-23 CH CH1040763A patent/CH471545A/de not_active IP Right Cessation
  • 1963-08-23 AT AT678563A patent/AT264996B/de active
• 1970
  • 1970-04-15 US US28215A patent/US3686003A/en not_active Expired - Lifetime

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