Patent GB-1068712-A (GB)
Title: Food products
Inventor: SCHOGT JAN CAREL MARINUS
IPC: A23L27/21
Filed: 1962-07-24
Abstract: The following hydrocarbons are prepared: Hexa-1,5-diene, in Example 6, by treating allyl chloride with Mg. metal in ether;  Hexa - 1,5 - diyne, in Example 6, by treating 1,2,5,6-tetrabromohexane in ether with sodamide in liquid ammonia;  Octa - 1,5 - diyne, in Example 6, by reacting hexa-1,5-diyne with ethyl iodide in ether in the presence of sodamide in liquid ammonia;  Hepta - 1,6 - diyne, in Example 8, by reacting sodium acetylide in liquid ammonia with 1,3-dibromopropane; Nona - 1,6 - diyne, in Example 8, by reacting hepta-1,6-diyne with ethyl iodide in ether in the presence of sodamide in liquid ammonia.ALSO:A cream- or butter-like flavouring principle for foods consists of the novel compounds cis-hept-4-enal and/or trans-hept-4-enal or precursor compounds which form the cis- or trans-hept-4-enal as by hydrolysis, oxidation or antoxidation in situ in the foodstuff, for instance during cooking or storage.  The following precursors are mentioned: (1) the diethyl acetal of cis- or trans-hept-4-enal; (2) cis- or trans-hept-4-en-1-ol; (3) cis-cis-octadeca-11,15-dienoic acid. cis-cis-octadeca-10,15-dienoic acid and their stereo-isomers, either as the free acids or in the form of their functional derivatives, such as the ethyl esters, triglycerides and partial glycerides, and alkali metal salts; (4) 2-amino-oct-5-enoic acid, which is particularly effective as a precursor during the heating or frying of foods if sugars or dicarbonyl substances are present; (5) the reaction product of hept-4 enal with an edible amino acid containing a primary amino group and a mercapto group attached to adjacent carbon atoms, or a polypeptide or protein derived from it, as exemplified by cysteine or b -lactoglobulin.  It is stated that cysteine and b -lactoglobulin react with the hept-4-enal apparently forming compounds with a thiazolidine ring. According to the examples: (1) cis-hept-4-enal is prepared by increasing the chain length of cis-hex-3-en-1-ol by one carbon atom through the bromide and nitrile to cis-hept-4-enoic acid and converting this to cis-hept-4-enal via the acyl chloride and N-methyl anilide; (2) cis-hept-4-enal diethyl acetal is prepared from cis-1romohex-3-ene; (3) cis-hept-4-enal is prepared from cis - hept - 4 - enal diethyl acetal; (4) trans-hept-4-enal diethyl acetal is prepared by converting trans-hex-3-en-1-ol into trans-1-bromohex-3-ene and converting the bromide into the acetal; (5) trans-hept-4-enal diethyl acetal is hydrolysed to trans-hept-4-enal; (6) cis-cis-octadeca-11,15-dienoic acid is prepared by first preparing hexa-1,5-diene from allyl chloride by a coupling reaction using magnesium, converting to hexa-1,5-diyne by bromination and dehydro-bromination, and replacing one of the active hydrogen atoms with an ethyl group to give octa-1,5-diyne, 1-chloro-9-iodononane prepared from 1,9-dichlorononane by exchange with sodium iodide is coupled with the octa-1,5-diyne through its remaining active hydrogen atom to give 1-chloro-heptadeca-10,14-diyne, 14-diyne, which is converted through the nitrile to octadeca-11,15-diynoic acid, and then by selective hydrogenation with a Lindler catalyst to the diene; (7) cis-cis-octadeca-11,15-dienoic acid is prepared by selective hydrogenation of 1-chloroheptadeca-10,14,diyne to cis-cis-1-chloroheptadeca-10,14-diene, which is then converted into a Grignard reagent and carbonated to give the desired acid; (8) cis-cis-octadeca-10, 15-dienoic acid is prepared by first producing hepta-1,6-diyne (from sodium acetylide and 1,3-dibromopropane) and converting this to nona-1,6-diyne, 1-chloro-8-iodo-octane is coupled with the nona-1,6-diyne through its remaining active hydrogen atom to give 1-chloroheptadeca-9, 14-diyne, this is converted by selective hydrogenation with Lindlar catalyst to cis - cis - 1 - chloro - heptadeca - 9,14-diene, which is finally converted to a Grignard reagent and carbonated to give the desired acid; (9) gives a preparation of cis-cis-octadeca-10,15-dienoic acid; and (10) gives a preparation of cis-2-amino-oct-5-enoic acid.  Examples 11 and 12 relate to the reaction products of cis-hept-4 enal with cysteine and b -lactoglobulin, respectively.ALSO:A precursor for the cream- or butter-like flavouring cis-hept-4-enal or trans-hept-4-enal giving the flavour during cooking or storage of food in which it is incorporated, consists of the reaction product of the hept-4-enal with an edible amino acid containing a primary amino group and a mercapto group attached to adjacent carbon atoms, or a polypeptide or protein derived from it, exemplified by cysteine or b -lactoglobulin. According to an example, b -lactoglobulin (0.5 g.) and cis-hept-4-enal (0.02 g.) were dissolved in water (20 ml.) and the solution was kept overnight in a refrigerator for the reaction product to precipitate out.ALSO:Cream- or butter-like flavour is imparted to, or enhanced in, margarine, products containing butter fat, shortenings, artificial cream, ice-cream, chocolate, soups, sauces, processed cheese, bakery products and ingredients, and confectionery such as sweets, toffees and fudge, by incorporating therein a minute proportion of cis-hept-4-enal or trans-hept-4-enal, or a precursor which forms the cis- or trans-hept-4-enal as by hydrolysis, oxidation or auto-oxidation in situ in the foodstuff, for instance during cooking or storage.  The following precursors are mentioned: (1) the diethyl acetal of cis- or trans-hept-4-enal; (2) cis- or trans-hept-4-en-1-ol; (3) cis-cis-octadeca-11, 15-dienoic acid or cis-cis-octadeca-10, 15-dienoic acid and their stereoisomers, either as the free acids or in the form of their functional derivatives such as the ethyl esters, triglycerides and partial glycerides, and alkali metal salts; (4) 2-amino-oct-5-enoic acid, which is particularly effective as a precursor during the heating and frying of foods if sugars or dicarbonyl substances are present; (5) the reaction product of hept-4-enal with an edible amino acid containing a primary amino group and a mercapto group attached to adjacent carbon atoms, or a polypeptide or protein derived from it, as exemplified by cysteine or b -lactoglobulin.  It is stated that cysteine and b -lactoglobulin react with the hept-4-enal apparently forming compounds with a thiazolidine ring.  Larger proportions (specified) of trans-hept-4-enal are needed than when the cis-form is employed.  The flavour imparted by the hept-4-enal may be supported by such additional flavouring agents as: (1) a lactone of a d - or g -hydroxy straight chain aliphatic monocarboxylic acid of from 8 to 14 carbon atoms, (2) diacetyl, or (3) a fatty acid of from 4 to 10 carbon atoms.  In order to obtain a margarine that develops the same flavour as butter on heating, a precursor such as octadeca-11, 15-dienoic acid or octadeca-10 15-dienoic acid may be employed in addition to the hept-4-enal.  In bakery products such as biscuits and cakes, and confectionery such as fudge, containing fat subject to autoxidation, the hept-4-enal is used in conjunction with a precursor giving rise to the free aldehyde on autoxidation.  A flavouring agent comprising hept-4-enal or its precursor in a refined edible oil may be applied to foods by dipping, sprinkling or spraying.  The flavouring compounds can also be applied to the crust of a bakery product or incorporated in foods by exposing them to a gas containing a sufficient amount of the vapour of the flavouring substance. According to the examples: (13) a flavouring agent for incorporation in margarine was made by dissolving in refined groundnut oil, d -hydroxy-n-dodecanoic acid lactone, d -hydroxy-n-butyric acid lactone, g -hydroxy-n-octanoic acid lactone, e -hydroxy-n-dodecanoic acid lactone, butyric, caproic caprylic and capric acids, diacetyl, acetyl methylcarbinol and cis-hept-4-enal; (16) there was incorporated into a vanilla ice-cream of 10% fat content, butyric acid, diacetyl and cis-hept-4-enal; and (20) shortbread was made from the following ingredients:- wheat flour, margarine, sugar, salt, baking powder, water and cis-cis-octadeca-11, 15-dienoic acid.