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Analysis of the Volatile Compoundsof Psidium cattleianum Sabine Fruitfrom Reunion IslandGaston Vernin a , Christian Vernin a , Jean ClaudePieribattesti b & Claude Roque ba Laboratoire de Chimie des Arômes-Oenologie, (CNRS ESA6009) Faculté des Sciences et Techniques de St-Jérôme ,Avenue Escadrille Normandie-Niémen, Case 561, 13397,Marseille Cédex 20, Franceb Laboratoire d'Agrochimie, Faculté des Sciences , Universitéde la Réunion , B.P. 7151, 97715 St-Denis Messag, Cédex 9,La Réunion, FrancePublished online: 09 Dec 2011.

To cite this article: Gaston Vernin , Christian Vernin , Jean Claude Pieribattesti &Claude Roque (1998) Analysis of the Volatile Compounds of Psidium cattleianum SabineFruit from Reunion Island, Journal of Essential Oil Research, 10:4, 353-362, DOI:10.1080/10412905.1998.9700923

To link to this article: http://dx.doi.org/10.1080/10412905.1998.9700923

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J. &sent. Oil Res., 10, 353-362 (Jul/Aug 1998)

RESEARCH REPORT

Analysis of the Volatile Compounds of Psidium cattleianum Sabine Fruit from Reunion Island

Gaston Vernin* and Christian Vernin** Laboratoire de Chimie des Admes-Oenologie, (CNRS ESA 6009,)

Facult6 des Sciences et Techniques de Stj6r6me Avenue Escadrllle Normandie-Ni6men, Case 561, 13397 Marseille C6dex 20, France

Jean Claude Pieribattesti and Claude Roque Laboratoire d'Agrochimie, Facult6 des Sciences, Universit6 de la Rkunion, B.P. 7151

97715 St-Denis Messag, C6dex 9, La R6unZon, France

Abstract Volatile aroma compounds from red (Psidium cattleianum, Sabine) and yellow

(Psidium cattleianum, Sabine, var. lucidum Hort.) guava fruits were analyzed by GC and GUMS. Among the compounds identified were: 31 hydrocarbons, 9 acetals, ethers and oxides, 13 aldehydes, 13 ketones, 30 esters, 48 alcohols, 2 acids, 2 sulfur- containing compounds, 4 phenol derivatives, menthofuran and coumarin. The following compounds are thought to contribute to the aroma of the red fruit. Fruity notes are due to ethyl esters (C,-CI6), tiglates, cinnamates, while floral notes can be attributed mainly to terpenic alcohols, 2-phenylethyl alcohol, p-ionone and l-phenylpropane-l,2-dione. Spicy notes may be due to cinnamaldehyde, eugenol, methyl isoeugenols, while burnt notes are due to furfural and 2-acetylfuran. The herbaceous, slightly spicy-like odor can be attributed to 2-tridecanone and the sweet and balsamic notes to benzyl benzoate. The guava aroma is characterized by the quasi absence of lactones.

Key Word Index PsMium cattlebnirm, Myrtaceae, volatile constituents.

Introduction The Psldium genus (Myrtaceae), comprising more than 100 species, has its origin in the American

tropics and subtropics although by the early 17th century it had been distributed throughout Asia. P. cattleianrrm was exported from Brazil between 1818-1830 and introduced into Mauritius and Reunion where it now grows wild. It has several synonyms: P. vartabile Berg, P. littoral Raddi, P. indiu.m Boyer and P. chinense D.C., but it is commonly called the strawberry guava on account of its characteristic aroma. In French the fruits are called goyavters as opposed to those of P. guajava L. which are called goyaves. They are small trees or shrubs with green reddish-brown bark and tough leaves. They possess small reddish fruits about the size of a walnut. The shrubs grow preferentially in tight thickets in clear 'Address for correspondence "C. Vernin is at the present time working at the Reunion (CRI'IT Agro-alimentaire)

1041-2905/98/0004-0353$04.00/&@1998.Allured Publishing Corp

Received: Nouember 199G Reuised: April I997

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354

spaces on slightly fertile fallow-lands. Another variety P. cattlelanum var. lzicldum Hort. also grows in Reunion to a lesser extent. This

variety is similar to the red-fruited cultivar, although it yields slightly larger, less acidic yellow fruits that are more appreciated than the red-fruited type. The two cannot be confused with the P. guaua which is not present at the Reunion except under garden cultivation (1-3). Both fruits are liked not only for their medicinal properties where they are used to treat influenza conditions, severe stomach pains and bloody diarrhea due to their astringent power, but they are also liked for the flavors they impart when they are used either in their natural or processed forms in sherbets, ice cream, jellies, jams, etc. Fermentation of the ripe fruits yields an appreciated wine which, on distillation, gives a locally popular brandy. According to Wilson (4) the vitamin C content of P. cuttleianzim ranges from 11 to 50 mg/kg, while the reducing sugar content is 3% and caroten 0.1 mg/kg, respectively.

Because of their pleasant aroma, several studies have been devoted to the GUMS analyses of the volatile components of various P. guava cultivars. These results have been summarized by Shibamoto and Tang (51, Herrmann (61, and more recently by the TNO Institute (7). In contrast, only one earlier paper of Shiota et al. (8) deals with the volatile constituents of the two varieties of P. cattleianurn growing in Japan. More recently, Tucker et al. (9) studied the volatile leaf oils of five species of Psldium growing in America of which P. cattlelunum was one of the species studied. The foliar oil of P. cattleianzim was found to be rich in P-caryophyllene (60%). Other studies dealing with the biochemical (10) agrochemical (11) and agricultural (12) aspects of various species of P. cattlelanum (leaves and fruits) have been reported. As a follow-up to our recent work on P. gziajaua fruit aroma from Egypt (l3), we have studied the composition of the two fruit forms ofP. cattlelanzim from Reunion.

Experimental Plant Materfal: Red and yellow P. cattleianum fruits from Reunion island were taken by air to

Marseilles and immediately extracted. One sample of the red-fruited type was extracted in Reunion island. Sample Preparation: In Reunion island, small pieces of fresh fruits were put into a Bucchi

Rotavapor RE 111 (c) and a concentrate of the volatile aroma compounds was obtained in traps cooled in liquid nitrogen. In Marseilles, the fruits (4 kg) were sliced into small pieces and put into a flask with a mixture of pentane-dichloromethane (2/1: v/v) (1 L) and kept at the room temperature for two days with occasional stirring. After decantation, the solutions were dried over anhydrous sodium sulfate and distilled through a Vigreux column. The residue was analyzed by GC and GUMS. From yellow guava fniits a very weak quantity of aroma extract was obtained.

Routfne GC Analyses: An Intersmat IGC 120 FL gas chromatograph equipped with a flame ionization detector (FID) was used for routine GC analyses. A WCOT fused silica capillary column (50 m x 0.22 mm) coated with Carbowax 57 CB (film thickness 0.25 pin) was used. The oven temperature was kept 3 min at 70°C and then programmed to 210°C at a rate of 2'C/min. An ICR-1B Intersmat integrator was used to determine the GC peaks areas.

GC/MS: GC/MS analyses were carried out using a Ribermag R-10-10 combination mass spectrometer- gas chromatograph (DELSI 700) equipped with the EPA/NIH mass spectra data bank. A WCOT WAX 52 CB column (50 m x 0.32 nun, film thickness 0.25 pm) was used (inlet pressure: 1.8 bar). The column was kept 5 min at 70°C and then programmed to 210°C at 2"C/min. Mass spectrometer conditions were as follows: ionization voltage: 70 eV; emission current: 0.2 mA; ion source temperature: 150°C. From the red-fruited type of P. cattlelanzim extract obtained in Reunion island (File 2105) and in Marseilles (File 26091, 143 and 113 mass spectra were recorded, respectively. From the yellow-fruited extract 46 mass spectra were recorded.

Identification of Volatile Components: The identification of volatile aroma components of the guava samples was made by comparison of their retention indices on the polar column reported in literature (14,151 with those calculated from scans (16) and by comparison of their mass spectra from several data banks (14,17-19) or from the files available with our own SPECMA bank (20,21).

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PSIDIUM C~TIZE~ANLIM S- FRUIT FROM REUNION Ism 355

IKP: 1985

161

I204

0 20 40 60 80 100 120 140 160 180 200 220 240 260 280 300 320

El: 41(100) 119(97) 105(69) 161(61) 55(37) 81(34) 95(32) 82(30) 93(30) 204(29) 109(24) 69(24) 79(22) 91(22) 120(22) 39(22) 67(19) 53(17) 77(17) 107(17) 122(16) 83(14) 179(12) 205(6) 133(2)

IKP: 1996

0 20 40 60 80 100 120 140 160 180 200 220 240 260 280 300 320

El: 41(100) 4y64) lW(46) 69(42) 55(37) 79(29) 67(28) 93(28) 95(27) 105(25) 107(24) 81(21) 161(20) a 1 7 ) 121(16) 91(15) 71(14) 77(14) 83(14) 122(10) 204(10) 149(5) 189(3)

Figure 1. Mass spectra of two unidentified sesquiterpene derivatives

Results and Discussion Among 300 mass spectra recorded more than 154 volatile aroma compounds have been identified

in red and yellow guava (See Table I). Retention indices (RI) on the Carbowax 52 CB column are given. Shiota et al. (8) identified 35 (21) compounds in the fruits of red and yellow P. cattletunurn fruit volatile concentrates accounting for 52% and 60% of the concentrate, respectively. Monoterpene hydrocarbons with the exception of a-pinene, limonene and terpinolene have not been found here, neither were 3-phenylpropyl alcohol and its esters. Identified compounds can be divided into seven categories. Among the hydrocarbons, a greater number of alkyl benzenes (18) relative to monoterpenes (a-pinene, limonene and a-terpinolene) and sesquiterpenes (P-caryophyllene, a-humulene) were identified.

Several oxides, ethers and acetals were also present, trans- and cis-linalool oxides are well-known components of P. cattletunurn oils as well as p-caryophyllene, a-humulene and y-elemene, oxides. The diethoxy acetals were formed from ethanol and the corresponding aldehydes [hexanal, (2)- and (E)-Zhexenals, octanal, etc.1 present in the medium.

Among the alkyl ketones, we noted the presence of 2-tridecanone and 2-pentadecanone which possessed herbaceous and slightly spicy-like odors, and carvone and f3-ionone.

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356 G. VFXNIN FJT AL.

Table 1. Aroma compounds of the volatile concentrates of two different colored fruit varieties of Psidium cattleianum Sabine from Reunion

Occurrenced Occurrenced RIG Red Yellow Compoundsa.b RIG Red Yellow

Hydrocarbons (31) Aldehydes (13)

Aliphatics Heptane Decane Undecane Dodecane Tetradecane Pentadecane Hexadecane Heptadecane Octadecane Nonadecane

Toluene o-Xylene lsopropylbenzene p-Xylene Propylbenzene 1 -Ethyl-2-methylbenzene 1 -Ethyl-3-methylbenzene 1,2,3-TrimethyIbenzene 1 -Ethyl-4-methylbenzene p-Cymene 1,2,4-TrimethyIbenzene 1,3,5-TrimethyIbenzene ODiethylbenzene Naphthalene 2-Methylnaphthalene 1 -Methylnaphthalene

Aromatics@

700 1000 1100 1200 1400 1500 1600 1700 1800 1900

1050 1120 1160 1170 1198 1207 1210 1233 1237 1250 1268 1305 1325 1710 1810 1840

Mono- and sesquiterpenes a-Pinene' 1030 Limonene' 1195 Terpinolene' 1275 pCaryophyllene* 1600 a-Humulene" 1665

Oxides and Acetals (9)' 1,l -Diethoxyethane 1,l -Diethoxyhexane (Z)-1,l -Diethoxyhex-2-ene (E)-1 ,1 -Diethoxyhex-2-ene cis-Linalool oxide (F) 1,l -Diethoxyoctane trans-Linalool oxide (F) Caryophyllene oxide Humulene-1 ,2-oxide (11)

895 1232 1263 1272 1412 1428 1439 1910 1956

+ - + - + + + + + + + + + + + + - + + -

- + + + + + + - + - + - + - + - + - + - + - + - + + + + - + - +

+ - + - + - + + + +

+ - + - + - + - + - + - + - + + + -

Acetaldehyde Hexanal' (Z)-%Hexenal (E)-a-Hexenal' (E,E)-2,4-Hexadienal Nonanal Furfural aCarnpholene aldehyde Benzaldehyde* Neral Geranial (E,E)-2,4-Decadienal' (E)-Cinnamaldehyde

Ketones (13) 2-Butanone 2-Heptanone' 2-Methylcyclopentanone 4-Hydroxy-4-methyl-

pentan-Bone' 2-Nonanone Hydroxyacetone (acetoin) 2-Acetylfuran Carvone 1 -Phenylpropane-1 ,2-dione 2-Tridecanone p-lonone 2-Pentadecanone Salvia-4( 14)-en-1 -one

Esters (30) Ethyl acetate* Ethyl butyrate* lsoamyl acetate Ethyl hexanoate" Hexyl acetate* Ethyl 3-hexenoateg (Z)9-Hexenyl acetate" (E)-2-Hexenyl acetate (Z)-3-Hexenyl isobutyrate' Hexyl butyrate* Ethyl octanoate (2)-3-Hexenyl butyrate p-Menth-1 -en9-yl acetate Linalyl acetate Hexyl hexanoate'

700 1070 1122 1198 1365 1372 1424 1460 1496 1662 1726 1760 1970

890 1165 1255

1327 1365 1460 1462 1705 1770 1772 1880 1985 1990

+ + + + + - + - + - + + + - + - + + + - + - + - + -

+ + + + + -

+ + + - + - + - + - - + + - + - + - + -

870 + + 1030 + + 1107 + - 1220 + - 1250 + + 1286 + - 1295 + + 1314 + - 1365 + - 1405 + - 1421 + + 1445 + - 1474 + - 1544 + + 1605 + -

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PSIDIUM C~TIZELQNCJM SABINE FRUIT FROM REUNION ISLAND 357

Table 1. Continued

Compounds".b

Ethyl decanoate' (2)O-Hexenyl hexanoate' a-Terpenyl acetate Neryl acetate P-Phenethyl acetate (Z)-3-Hexenyl ester (2)-Ethyl cinnamate (E)-Ethyl cinnarnate (Z)9-Hexenyl tiglate (E)-Cinnarnyl angelate (2)-Cinnamyl tiglate Ethyl hexadecanoate (E)-Cinnamyl tiglate Diethyl phthalate' Ethyl isobutyl phthalate' Benzyl benzoate

Alcohols (48) Ethanol lsobutanol sec-Amy1 alcohol Butanol lsoamyl alcohol Amy1 alcohol 2-Hydroxypropanol 2-Heptanol Hexanol (E)+Hexenol (Z)-3-Hexenol* (Ej-2-Hexenol 3,5,5-Trimethylhexanol 2-Nonanol' Linalool" Octanol a- Fenchol 2,3,3-Trimethylbicyclo-

(2,2,1 )-heptan-Pol Terpinen-4-01' trans-p-Menth-2-en-l -ol

Occurrenced RIC Red Yellow RIc

1625 1650

1725 I 680

1780 I a95

2085 2070

21 25 2200 2220 2230 2240 2300 2430 2500

900 1065

1105

1216 1236

1320 1325 1350 1375

1506 1525 1530 1551

i 086

1185

1284

1480

1570 1575 1595

+ - + - + - + - + + + - + - + - + - + - - + + - - + + - + - + -

+ - + - + - + - + - + - + - + - + - + + + - + - + - + - + + + - + -

+ - + - + -

Occurrenced Red Yellow

2-Decanol trans-Pinocarveol a-Terpineol* Nerol' transCarveol p-Cymen-8-01 Geraniol' Benzyl alcohol Undecanol 2-Phenethyl alcohol 2-Tridecanol a-Humulen-7-01 Palustrol Cubenol (E)-Nerolidol* 2-Tetradecanol 1 0-epi-y-Eudesmol T-Cadinol An Eudesmol isomer A Naphthalenol Cedrol a-Cadinol (I) a-Muurolol (2)-Cinnamyl alcohol P-Eudesmol a-Cadinol (11) (E)-Cinnamyl alcohol

Miscellaneous Acetic acid Hexanoic acid lsopropyl propyl disulfide Dipropyl trisulfide Menthofuran Methyl eugenol (2)-Methyl isoeugenol (E)-Methyl isoeugenol E u g e n o I Coumarin

1615 1620 1670 1 755

1790 1796

1787

1 aoa 1 a30 1 a35

1938

1980

1866

1967

2000 2093 2120 2145 21 50 2160 21 74 21 ao 21 a5 21 97 2200 2210 2215

1408 i 785 1240 1520 1694 1960 2002 2033 21 10 2350

+ - + - + - + - + - + - + - + - + - + - + - + - + - + - + - + - - + + - + - + - + - + - + - + - + - + - + -

+ - + - - + - + + - + - + - + - + - + -

~ ~

Wain components are given in bold: %ompounds identified by Shiota et al. (8) are indicated by an asterisk. In an extract obtained by steam distillation, they reported the presence of: myrcene. a-terpinene, (Z)- and (E)-ocimenes, y-terpinene. allo-ocimene, P-terpenyl acetate, a-copaene, 3-phenylpropyl alcohol and its esters (acetate, propionate, butyrate) which have not been found in the present study; 'Calculated from scans using linear alkanes as reference compounds (polar column); dResults obtained from two red P. cartleianurn samples extracted in Reunion and in Marseilles, respectively. The yellow-fruited sample was only obtained in Marseilles, in a very low amount due to a low quantity of extracted fruit; 'Three alkylbenzenes (MW 134 with a base peak at mlz: 134) have been also found; 'Several linear or cyclic acetals with base peaks either at mlz 45 or 59 were also present: Correct isomer not identified; hSeveral sesquiterpenic derivatives remain unidentified. Their analytical data are reported in Table II; Iprobable artifacts

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358 G. VERNIN ET AL.

IKP: 2225

0 20 40 60 80 100 120 140 160 180 200 220 240 260 280 300 320

El: 41(1W) 187(62) 43(45) 202(32) 55(28) 69(27) 91(21) 107(20) 79(20) 93(19) 53(17) 131(17) al(l6) 67(15) 105(15) 77(13) 123(13) 145(13)95(13) 120(8) 159(6) 203(5) 173(4)

IKP: 2160

0 20 40 60 80 100 120 140 160 180 200 220 240 260 280 300 320

El: 161(1W) 41(85) 91(61) 105(49) 29(46) 93(44) 187(40) 55(38) 205(37) 79(37) 107(32) n(29) 119(29) 159(25) 162(24) 53(21) 131(20)67(18)69(18) 117(16)81(16)95(14) 145412) 133(11)PO(7) 123(6)202(3)

Figure 2. Mass spectra of two unidentified sesquiterpene alcohols

Aliphatic esters such as the even ethyl esters (C, to CJ, hexyl- and hexenyl-, butyrates and hexanoates, tiglates [3-hexenyl and (2)- and (E)-cinnamyl], (2)- and (El-ethyl cinnamates, benzyl benzoate play an important role on the fruity notes of the guava aroma. Terpenic acetates (linalyl, a-terpinyl, neryl, geranyl) have also been found.

By far, the alcohols constituted the most important category of compounds. Besides the usual terpenic alcohols such as linalool, terpinen-4-01, a-terpineol, nerol, and geraniol which were responsible for the floral notes, we found benzyl-, 2-phenylethyl-, (2)- and (El-cinnamyl-, alcohols and their corresponding acetates. Sesquiterpenic alcohols also constituted an important class of compounds which included palustrol, a copaenol, eudesmol isomers, a-, and T-cadinols, a-muurolol etc.

Phenols such as eugenol and methyl isoeugenols and cinnamaldehyde contributed to the spicy notes of the aroma. Furfural and 2-acetylfuran arising from thermal degradation of reducing sugars (as well as hydroxyacetone and acetoin) possessed burnt notes. Sulfur-containing compounds (isopropylpropyl disulfide, dipropyl trisulfide) which have very low threshold values were responsible for the burnt, earthy and sulfurous odors. Several compounds of this kind have been reported as minor components responsible for the guava aroma (22). The green odor of cut hay was thought to be due to coumarin.

The acidic fraction which was rather small, included only acetic and hexanoic acids. Numerous other

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PSIDIUM C A T ~ ~ L A N U M SABINE FRUIT FROM Rmrmo~ ISLAND 359

IKP: 2430

80-

60-

40-

20 - 0 -

-EI 41

43 55

67

81

44 54 95 a0

b9z 57 96 109 149

1124 13) , , , , , , , * , , ~ , * , , , , , , , , , , , , , , , . , , , . , , . , , , , ,',Y.l ;,-,. , I .';:: 1 1 , I , I I , I I I I , I r r + I

0 20 40 60 80 100 120 140 160 180 200 220 240 260 280 300 : El: 41(lW) 43(90) 55(87) 67(64) 81(48) 44(45) yY41) 95(39) a(%?) 66w) 82(28) 79(25) V(20) Iog(19) 98(18) 149(18) 135(13) 124(11) 308(3) 216(3) 164(2) 178(2) 191(2)

IKP: 0

0

0 20 40 60 80 100 120 140 160 180 200 220 240 260 280 300 320

El: 57(1W)56(95)43(79)41(70)55(28)60(15)285(13)73(13)83(12) 105(10)85(10) 117(8)267(8) 1 1 6 ( 8 ) 9 1 ( 7 ) 2 ~ 162(6) 107(5) 147(5) 95(5) 340(3) 185(3)

Figure 3. Mass spectra of two unidentified diterpenoids

minor compounds have not been identified. We believe that the olfactive properties of the red-fruited P. cattlehnum can be divided in three main categories. The predominant one was a fruity odor characteristic of the wild strawberry with passion fruit, cherry, peach and mango-like notes. The second one was a green odor with grass-like note, and the third one possessed a floral odor with a rose-like note due to geraniol and 2-phenethyl alcohol.

Among other interesting compounds, (2)- and (El-cinnamyl tiglates as well as (E)-cinnamyl angelate have been identified. Angelates and tiglates are well-known components of Roman camomile (Anthemis n o b W and several of their mass spectra have been published (23,241.

As angelates and tiglates are very similar, Thomas and Willhalm (23) proposed to take into account the ratio of the two fragments at m/z 83 and 82. This ratio seems to be higher for the (E)-isomer (tiglate) relative to the (2)-isomer (angelate) allowing the two isomers to be distinguished. In our case, the ratio for cinnamyl angelate is equal to =3, while for the two cinnamyl tiglates it is higher than 100. The differentiation between (2)- and (E)cinnamyl derivatives was also based upon their retention indices. The retention index for the (2)-isomer is less than that of the (E)-isomer. These compounds have not been found in the aroma of P . gzrajaua fruits (13). Unidentified sesquiterpenic compounds and their

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360 G.Ve~~mer.41..

Table II. Analytical data for unidentified sesquiterpenic derivatives in Psidium cettleienum red fruit from Reunion

Sesquiterpenic Derivatives RI* MW m/zb

C15H240 1875 220 41,96,79,43 1880 ? 57,43,71,55

a-Humulenot ? 1893 222 41,43,93,81,55,69 1933 ? 41,43,69,79,91,109 1951 ? 43,69,81,95,109,122

Epoxy-y-Elemene ? 1917 220 79,93,41,39,105,120 1921 ? 69,68,41,39,43 1925 ? 41,43,91,79,69

A Bourbonol ? 1964 222 81,121,108 1980 ? 57,43,71,55 1987 222 ? 43,93,81,109,121 1996 ? 41,43,109,93 2003 ? 43,41,127,120,155

Tetramethyl octahydrod-azulene methanol 2005 222 41,161,105,107,91 2010 ? 179,94,79,41,43 2024 222 43,41,119,161,105, 2026 ? 43,41,67,59,149

1,1,4,7-TetramethyI-(l H)-cycloprop-azulen-4-ol ? 2050 222 43,41,79,105 2080 ? 57,43,55,71

(C15H260) 21 90 222 43,41,55,95 21 95 220 43,95,59,105 2220 222 43,41,135,81

2240 ? 41,136,43,55,69 2280 234 ? 41,55,43,69,55,53 2374 ? 41,126,97 241 6 208 ? 43,135,151,44 2482 ? 108,43,45,41

(C, 5 4 4 0 ) (C15H,0) (C15H240) 2225 220 41,187,202

See caption Table I; Classified in decreasing order of intensity

analitycal data are reported in Table 11. A quantitative analysis of the volatile compounds of the red-fniitedp. cuttleiunum type from Reunion

is shown in Table 111. The observed differences between the composition given by Shiota et al. (8) and that reported here can be easily explained by the fact that the Japanese authors obtained an aroma concentrate by steam-distillation, while we used apolar solvent extraction method. In the first case the formation of terpene derivatives is favored by hydrolysis of disaccharides bonded to terpenes (25,26).

Quantitatively, the major components were aliphatic esters ( ~ 3 0 % ) followed by aliphatic alcohols (~14%). Terpenic alcohols (linalool, terpinen-4-01, a-terpineol, geraniol) content is rather low (=4%) as well as aliphatic ketones (~2.5%). Sesquiterpenic derivatives account for &lo%. This composition was quite different from that of guava fruit from other countries.

Mass spectra of six unidentified sesquiterpenoids and diterpenoids are reported in Figures 1-3. They have been reconstructed from our SPECMA 2000 data bank. The qualitative and quantitative compositions of the red-fruited P. cuttleiunum fruits extracted either on the growing area (Reunion) or in Marseilles are complementary. Further, the composition of the yellow-fruited type was found to be different from the red one, particularly by the presence of two sulfur compounds.

In contrast totheP.gzujuuu fruit aroma from Egypt studied (91, the absence of lactones is noticeable. Tiglates and cinnamates were olfactorily important as were other aroma substances reported here. The red fruit aroma could be of interest to the flavor industry as a flavor for shehers, ice cream, sweets, jam, brandy, etc.

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PSIDIUM CATIXEUNUM SABINE FRUIT FROM REUNION ISLAND 361

Table 111. Composition of the volatile extract of the red-fruit type of Psidium caffleianum from Reunion colored fruit’

Compounds Percentage Compounds Percentage

Ethyl hexanoate Ethyl acetate lsoamyl alcohol (+ 2-methylbutyl alcohol) 1 -Amyloxy-1-ethoxy ethane (2)-3-Hexenyl acetate (E)P-Hexenal diethyl acetal Hydroxylated alkyl ether derivative

(RI=1803, m/z:43,56,59,71,89) An heavy unsaturated ketone ?

(Rl=2369, m/z:41,126,97,53,69,81) Ethyl octanoate Linalool 2-Tridecanol Hydroxylated alkyl ether derivative

(RL1760, rnh:45,42,31,59,89) Caryophyllene oxide Carvone 1,l -Diethoxy ethane P-Caryophyllene Hydroxylated alkyl ether derivative

(RI=1819, m/z:59,45,31,103) Ethyl butyrate lsobutanol (E)-l,1 -Diethoxyhex-2-ene Hexanal (2)-3-Hexenol p-Phenethyl alcohol 2-Tridecanone (E)-2-Hexenal Acetic acid Unidentified

(2)9-Hexenyl butyrate (2)-Ethyl cinnamate Hexyl acetate Unidentified

1,l -Diethoxyhexane Globulol

(R=1814, m/z:43,71,56,83,98,143,173)

(Rl=2436, m/z:41,43,55,67,81,95)

(RI=2110, m/z:43,41,55,69,105,161, 1 1 9,133,147,189,204)

7.8 6.0 5.7 4.6 4.1 4.1

3.8

3.5 3.5 3.2 3.0

2.8 2.8 2.6 2.6 2.5

2.4 2.3 2.1 2.0 1.8 1.5 1.5 1.4 1.3 1.3

1.2 1 .o 1 .o 1 .o

0.9 0.8

0.8

(2)-1,l -Diethoxyhex-Pene Ethyl decanoate (E)-Cinnamaldeh yde Neral P-Phenethyl acetate (E)-Cinnamyl alcohol Eugenol [+ (E)-ethyl cinnamate] epi-a-Cadinol Sesquiterpenic alcohol (MW: 222) (Z)-Ethyl-3-hexenoate a-Humulene Hydroxylated alkyl ether derivative

Hydroxylated alkyl ether derivative

2-Pentadecanone epi-a-Muurolol A Sesquiterpenic derivative

2-Nonanone Coumarin n-Nonanal 2-Undecanone a-Terpinyl acetate Hexyl butyrate Terpinen-4-01 a-Terpineol Benzyl benzoate (2)- and (E)-lsoeugenols Hexyl hexanoate Geraniol Hexanoic acid P-Eudesrnol Naphthalene Ethyl hexanoate Linalool oxides (F) Methyl isoeugenols

(RI=1818, m/z:59,45,31,41,43,103)

(RI=1817, m/z:59,45,31,43,103, MW:

(RI=2210, rn/z:41,43,187,202)

Total (“A)

0.7 0.7 0.6 0.4 0.4 0.4 0.4 0.4 0.4 0.3 0.3

0.3

192) 0.3 0.3 0.3

0.3 0.3 0.3 0.3 0.3 0.3 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.1 0.1 0.1 0.1

97.7

.The solvent, ethanol, and the phthalates have not been taken into account; the amounts of minor compounds (~0.1%) hava nnt hnnn rmnrtd

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362 G. VER" ET AL.

Acknowledgments The authors are indebted to Dr. R. Stevens for comments and corrections, Mrs. C. Charlot for the GUMS

service, Mrs. G.M.F. Vernin for assistance with GC analyses, Mrs. R. M. Zamkotsian for help with the bibliography, Mrs. A. Monnerville, and Dr. B. G. Maiya for help with the English corrections of the paper.

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