gaims Translation Series No Original title: Autoxidationsverhalten von TritetradecylglycerinNther im Vergleich zu Trimyristin und Kokosa

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1 It Wee,. gaims FISHERIES AND MARINE SERVICE Translation Series No Autoxidation behavior of tritetradecyl glycerol ether by comparison with glyceryl trimyristate (trimyristin) and coconut oil by V. Miller Original title: Autoxidationsverhalten von TritetradecylglycerinNther im Vergleich zu Trimyristin und Kokosa From: Fette Seifen Anstichm. 78(10): , 1976 Translated by the Translation Bureau e MA) Multilingual Services Division Department of the Secretary of State of Canada Department of the Environment Fisheries and Marine Service Halifax Laboratory Halifax, N.S pages typescript

2 I^a vh H-391 L1- DEPARTMENT OF THE SECRETARY OF STATE TRANSLATION BUREAU MULTILINGUAL SERVICES DIVISION I!ff CANADA SECRÉTARIAT D'ÉTAT BUREAU DES TRADUCTIONS DIVISION DES SERVICES MULTILINGUES TRANSLATED FROM - TRADUCTION DE AUTHOR - AUTEUR Müller, V. German INTO - EN English TITLE IN ENGLISH - TITRE ANGLAIS Autoxidation behavior of tritetradecyl glycerol ether by comparison with glyceryl trimyristate (trimyristin) and coconut oil TITLE IN FOREIGN LANGUAGE (TRANSLITERATE FOREIGN CHARACTERS) TITRE EN LANGUE ÉTRANGÉRE (TRANSCRIRE EN CARACTÈRES ROMAINS) Autoxidationsverhalten von Tritetradecylglycerinâther im Vergleich zu Trimyristin und Kokosdl. REFERENCE IN FOREIGN LANGUAGE (NAME OF BOOK OR PUBLICATION) IN FULL. TRANSLITERATE,FOREIGN CHARACTERS. REFÉRENCE EN LANGUE ^TRANGERE (NOM DU LIVRE OU PUBLICATION).,4U COMPLET, TRANSCRIRE EN CARACTÈRES ROMAINS. Fette-Seifen-Anstrichmittel REFERENCE IN ENGLISH - RÉFÉRENCE EN ANGLAIS Fats - Soaps - Paints PUBLISHER- ÉDITEUR not given PLACE OF PUBLICATION LIEU DE PUBLICATION r, YEAR ANNEE 1976 DATE OF PUBLICATION DATE DE PUBLICATION VOLUME ISSUE N0. NUMÉRO 10 PAGE NUMBERS IN ORIGINAL NUMEROS DES PAGES DANS L'ORIGINAL NUMBER OF TYPED PAGES NOMBRE DE PAGES DACTYLOGRAPHIÉES 8 REQUESTING DEPARTMENT Environment TRANSLATION BUREAU NO. MINISTÈRE-CLIENT NOTRE DOSSIER NO BRANCH OR DIVISION DIRECTION OU DIVISION Fisheries TRANSLATOR ( INITIALS) TRADUCTEUR (INITIALES) MM,A PERSON REQUESTING dllo-. rp 7?o4A (',.- h (A ( fl 0d cl-1 YOUR NUMBER VOTRE DOSSIER NO 3 AN 2o AIR December DATE OF REQUEST DATE DE LA DEMANDE 3 SOS (RF V. 2/88) UNrDÎ1 i.;l.j Tiâr cn1.raîion For inf'c:-niin";on only TRAi?:!C'i4o,? NON MEVISEF Informa;-ion seulerrcnf

3 , DEPARTMENT OF THE SECRETARY OF STATE 4 TRANSLATION BUREAU SECRÉTARIAT D'ÉTAT BUREAU DES TRADUCTIONS F4-rw 43W4 MULTILINGUAL SERVICES DIVISION CANADA DIVISION DES SERVICES MULTILINGUES CLIENT'S NO. NO DU CLIENT DEPARTMENT MINISTERE DIVISION/BRANCH DIVISION/DIRECTION CITY VILLE Environment Fisheries 14 A-lC BUREAU NO. NO OU BUREAU LANGUAGE LANGUE German MM,A.. TRANSLATOR(INITIA LS) TRADUCTEUR ( INITIALES) 1977 vt Muller, V.: Autoxidationsverhalten von Tritetradecylglycerinâther im Vergleich zu Trimyristin und Kokosôl. [Autoxidation behavior of tritetradecyl glycerol ether by comparison with glyceryl trimyristate (trimyristin) and coconut oil]. Fette-Seifen-Anstrichmittel Z8: #10, (1976). ABSTRACT Tritetradecyl glycerol ether is consjderably less stable towards atmospheric oxygen than glyceryl ^myristate and coconut oil: During the storage of tritetradecyl glycerol ether at 600 C up to 96 hours, the peroxide value. increases continuously after an incubation time. Under the same conditions, the peroxide value of a reference sample containing 500 ppm of a-tocopherol did not increase. Upon heating to 1800 C the tritetradecyl glycerol ether is degraded much more rapidly than glyceryl myristite and coconut oil. Chiefly polar reaction products are being formed, according to liquid and gel permeation chromatography presumably mono- and dialkyl glycerol ethers, tetradecanal, tetradecanol and further compounds not yet identified. The reaction products, in part, possess a higher molecular weight than the original compound. The resolution of the reaction products by liquid chromatography is described. From the Unilever Research Association, Hamburg Author`s address: Dr. V. Müller, Unilever Forschungsgesellschaft mbh, Behringstrasse 154 D2000 Hamburg50 WEST GERMANY ElNM4, ;:4:y a. F 1 5 { TRADUCTION NON VZEil?SEF l.mfor:wafjcan saarl:ÿt;ie* SOS

4 t 1. INTRODUCTION It has been proposed that trialkyl glycerol ether be used as substitute for dietary fats to reduce thecaloric content of foodstuffs (1). Apart from that, such compounds may also become useful as markers in clinical and diagnostic fat absorption studies (2-4). We have investigated the autoxidative behavior of tritetradecyl glycerol ether upon storage and under thermic stress in the presence of air. Trymiristin (glyceryl trimyristate) and coconut oil were used for comparison. 2. MATERIAL Tritetradecyl glycerol ether (TTG) was prepared from tetradecyl bromide and glycerol according to the method described in reference #5. Part of the sample was deodorized at 180 C at a water throughput of 60%. Peroxide values of the samples, according to Wheeler, were 1.7 prior to deodorization and 1.3 after deodorization or 3.5 respectively after three months of dark storage of the deodorized sample at 15 C under nitrogen. The melting point of the sample crystallized from hexane (as gleaned from TLC heating curves) amounted to 35.5 C, following solidification from the melt C. The gas-chromatographically determined purity of the sample was 95.9%; for further details the reader is referred to Table 2. Coconut oil is the plant fat most closely resembling TTG with respect to melting point, molecular weight and chain length. The commercial product used showed a climbing melting point of 26 C and - according to the results obtained by gel permeation chromatography (GPC) - it contained 98.3% of triglycerides, of these 80.5% were medium chain triglycerides, corresponding to a molecular weight of approximately 680, and 17.8% long-chain triglycerides. Trimyristin is equivalent to TTG in chain length. Due to esterfication, the molecular weight and the melting point (57.5 C) are considerably higher than they are in TTG. GPC revealed that the sample used contained 96.8% of triglycerides and 1.5% of diglycerides 3. METHODS AND RESULTS 3.1 Experiments done for general orientation Experiments for the purpose of general orientation on the autoxidation of tritetradecyl glycerol ethers were carried out with 1 g samples with a surface of approximately 16 cm 2/g, By the end of 2

5 4 hrs. the following peroxide values were found: at , 413 at 100 C - 59, at 150 C - 71; after 20 hrs. at 150 C After 4 hrs. 150 C, GPC revealed that only 47% of unaltered tritetradecyl glycerol ether was still present; most of the evolving reaction products were low molecular compounds. After 20 hrs./150 C the proportion of compounds whose molecular weight corresponds to oligomers of the trialkoxylipid had increased substantially. 3.2 Storage at 60 C Duplicate samples of 3 g of TTG, trimyristin or coconut oil respectively were subjected to the "Schaal" test (6) and stored in the drk at 60 C for 4,8,16,24,48 and 96 hrs. in roller panel jars * air access) - at a surface of approximately 1.3 cm 2/g. The (with "Schaal" test was repeated three months later on heated TTG with or ** without the addition of 500 ppm DL-a-tocopherol. The course of autoxidation was checkèd on 1 g portions of each sample by determining the peroxide value according to Wheeler (Table 1). Thin layer chromatographic evaluation was done on ready made 414 silica gel plates of the Merck Company (0.25 mm). Solvent used: petroleum ether/ether/glacial acetic acid (90/10/1)(v/v). Plates were stained with 10% phosphomolybdic acid in ethanol; subsequently they were heated to 180 C. In the steamed TTG samples the induction period amounted to approximately 16 hrs. In TTG samples which had not been steamed the peroxide value climbed constantly without any discernible induction period. The peroxide value of the triglycerides used as reference compound remained unchanged. Following addition of 500 ppm of DL-atocopherol to the TTG the peroxide value remained unalterably low during a 96 hr. period of storage. After 24 hrs. TLC of TTG without added tocopherol revealed polar reaction products whose Rf-values were equivalent to those of ditetradecyl glycerol ether. The slightly nutty flavor of TTG increased during storage; after 24 hrs. a 'green' foreign taste - presumably of tetradecanal - was clearly discernible. The TTG samples to which tocopherol had been added only underwent *height 65 mm, external diameter mm, internal diameter mm, Besser Co. - ** Merck Co. Arlicle #

6 e 4 Table 1: Changes in peroxide values (in meq 0 9/kg) of tritetradecyl blycerol ether, coconut oil and trimyristin during storage at 60 0 C Lagerung Tritetradecylglyceriniither Kokosiil Trimy- bei 60 C unge- gedâmpft ristin (h) dâmpft mit ohne 500 ppm Tocopherol , * after 3 monins storage of the steamed sample at 15 C in the dark. Lagerung bei = storage at; ungedgmpft = unsteamed; gedgmpft = steamed; ohne = without; mit = with. (For Table 2 = see p.5) Table 3: Decomposition products of tritetradecyl glycerol ether after 0, 8 and 40 hrs. at 180 0C, determined by liquid chromatographic separation. Retentionszeit = retention time; Flechen-% = surface % Vermutete Substanz = presumed substance; stark polare Verunreinigungen, z.t. Untergrund = strongly polar cnntaminats, partly background. Retentionszeit Flâchen-% 0h 8h 40h Verniutete Substanz Tetradecanal Di tetradecylâther Tritetradecylglyceriniither DitetradecyIglycerinâther Tetradecanol Monoalkylglycerin- Wher, stark polare Verunreinig-ungen, z. T. Untergrund

7 I 5 Table 2: Changes in tritetradecyl glycerol ether, trimyristin and coconut oil during storage at 1800C. TritetradecylglycerinHther vor nach nach Dâmpfen Trimyristin Kokos81 Diimpfen Di;mpfen mit u-tocopherol Belastungsdauer bei 1800 C (h) 0 S GPC-Bereidre (11. lo) Dimere und Verbindungen hsherer Molekulargewichte ;. IVlonomere Ausgangsverbindung(en) (Triglyceride bzw Tritetradec YgY 1 1 cerinïfher) S.3'r:r * 851.7" Ditetradecylglycerindther bzw. Diglyceride, Dialkyldther bzw. Verbindungen entsprechender Molekulargewichte Sonstiges LC-Bereiche (Tl. lo) unpolarer als Ausgang Ausgangsverbindung polarer als Ausgang Aussehen farblos gelb braun farblos gelb Sclnnelzpunkt (Tottoli) (OC) Steigsclmielzpunkt ( C) gelb farblos fahl- farblos schwach gelb gelb * Solvent tetrahydrofurane; ## solvent CH2CL2; ### see text. vor = prior to; nach = after; D&mpfen = steaming; mit = with; Kokos8l = coconut oil; Belastungsdauer bei...duration of stress at...; Bereiche = ranges; Dimere und Verbindungen h8herer Molekulargewichte= dimers and com ounds with higher molecular weights; Monomere Ausgangsverbindung^en) = monomeric initial compound(s) ; bzw. = respectively;^^ VVIkA Verbindungen entsprechender Molekulargewichte = compounds with corresponding molecular weights; Sonstiges = other; unpolarer als Ausgang = more unpolar than initial (compound); Ausgangsverbindung = initial compound; polarer als Ausgang = more polar than initial (compound); Aussehen = appearance; farblos = colorless; gelb = yellow; braun = brown; fahlgelb = feeble yellow; schwach gelb = slightly yellow; Schmelzpunkt = melting point; Steigschmelzpunkt = climbing melting point.

8 ' a very minor change in taste Thermic oxidative stress at 180 C 3 g samples of TTG, trimyristin and coconut oil were stored for 8, 16, 24 and 40 hrs. at in the dark in rolling wall jars allowing access to air. Subsequently they were cooled under a N2 atmosphere. A reference sample of TTG (8 hr. storage) containing 500 ppm of DL-a-tocopherol was used. The molecular weight distribution of selected samples was determined by GPC according to the method described in reference #7. For high pressure liquid chromatography (HP-LC), the substances dissolved in CC14, put on steel columns (4.5 x 300 mm) filled with Lichrosob SI 60, granule size 5 gm, were separated with two successive solvent gradients: Solvent I = heptane: = 32:68; II = heptane: water-saturated CHC1 :dioxane = 19:77:4; III = water-saturated CHOI :ethanol 3 = 3 75:25. LC separation of thermic-oxidative degradation products of tritetradecyl glycerol ether has already been described and reported in reference #8. LC determination of the unaltered triglycerides of coconut oil was done according to the method described in reference #9. As early as after 8 hrs. of storage at 180 C 23% of the steamed and 28% of the unsteamed tritetradecyl glycerol ether were found to be decomposed (Table 2). Reaction products were overwhelmingly more polar compounds than TTG (LC - Table 3); GPC revealed that more compounds with lower molecular weight than compounds with higher molecular weight had evolved. By the end of 40 hrs. 87% of the TTG had disintegrated (LC - Table 3). The decomposition products, such as aldehyde, alcohol, dialkyl ether, monoglycerol ether and dialkyl glycerol ether have also been observed as secondary products in the synthesis of tritetradecyl glycerol ether (5). Adding DL-a-tocopherol only reduces the decomposition of the alkoxylipid to an insignificant extent (Table 2). In trimyristin and coconut oil the proportion of unaltered triglycerides found fter 8 hrs. at 180 C had been reduced by 3.9% and 8.6% respectively (Table 2). In coconut oil the medium chain triglyceride moiety remained constant with 80.5%, while the proportion of long-chain triglycerides declined from 17.8% to 9.1%.

9 7 For the most part, the new compounds evolving were dimeric compounds. 4. DISCUSSION Both at 60 C and at 190 C the saturated tritetradecyl glycerol èther is less stable to autoxidation than trimyristin or coconut oil. It may therefore be assumed that TTG will undergo more rapid oxidative changes even under storage conditions normally encountered by fat and fat products. Although the positive influence exerted by tocopherol at 60 C suggests that an admixture of plant oils with high tocopherol levels might reduce the rate of TTG oxidation to some extent, the oxygen sensitivity of TTG at higher temperatures is not very auspicious, and its technical use as a non-caloric exchange for frying fats, for example, does not seem to offer a realistic advantage. 11 The author is indebted to Dr. K. Aitzetmûller and colleagues for elaborating and carrying out the liquid chromatography, Dr. M. Unbehend and colleagues for gel permeation chromatography, and Mrs. M. Patzig for careful and conscientious collaboration. Received August 19, 1976.

10 8 REFERENCES 1 H. K. Mangold in: Ether Lipids, Chemistry and Biology, F. Snyder, Ed., Acad. Press, New York, London 1972, S F. Paltauf, F: Spener, Chem. Phys. Lipids 2, 168 [1968]. 3 W. E. Carlson u. H. S. Bailey, Brit, J. Nutrit. 28, 295 [1972]. I?. G. H. Morgan u. A. F. Hofmann, J. Lipid Res. 11, 223 [1970]. 5 V. Muller, Publikation in Vorbereitung. N. T. Joyner u. J. E. McIntyre, Oil and Soap 15, 184 [1938]. 7 M. Unbehend, H. Scharmann, Straufi u. G. Billek, Fette Seifen Anstrichmittel 75, 689 [1973]. 8 K. Aitzetmiiller, J. Chromatogr. Sci. 13, 445 [1975]. D K. Aitzetniiiller u. G. Guhr, Fette Scifen Anstrichmittel 78, 83 [1976]. Publikation in Vorbereitung = publication in preparation.

FISHERIES AND MARINE SERVICE. Translation Series No Investigation of the lipid composition of several species of fish

FISHERIES AND MARINE SERVICE. Translation Series No Investigation of the lipid composition of several species of fish FISHERIES AND MARINE SERVICE ARCHIVES Translation Series No. 3637 Investigation of the lipid composition of several species of fish by A.G. Rudenko, and V.I. Lisovskaya Original title: Issledovanie sostava