Indian Journal of Chemistry Vol. 398, December 2000, pp. 883 - 893

Review Article

The triterpenoids and steroids from Mangifera indica Linn

v j\njaneyulu* & P Radhika

Department of Organic Chemistry, School of Chemistry,

Andhra University, Visakhapatnam 530 003, India

The triterpenoid and steroid constituents of M. indica have been reviewed. Thirty four new triterpenoids have been reported from various parts of it. The variation of triterpenoid and steroid constituents of stem-bark from different regions of India is presented.

Mangifera Linn is a fairly large genus of evergreen trees of Anacardiaceae family. Three or four species are recorded in India, of which Mangifera indica is by far the best known and widely cultivated for its fruit.

M. indica Linn, is popularly known as 'the Mango' (Sanskrit : amra, chuta; Hindi: Am, amb., Telugu : Mamidi, mavi) is a large evergreen tree, 10-45 m height, with a heavy dome-shaped crown and a straight, stout bole, thick bark, rough, dark grey, flaking off when old, leaves linear, oblong or elliptic lanceolate, 10-30 cm long and 2-9 cm wide emitting when crushed -an aromatic, resinous odour. The mango is the most popular and the choicest fruit of India and occupies a prominent place among the best fruits of the world.

Mangoes are grouped under two broad categories: seedling types (wild and cultivated) and horticultural clones, propagated by budding or grafting. A large number of mango trees, estimated at over 1000 types are grown in various parts of India, each having its own peculiar taste, flavour and consistency of pulp. A comprehensive survey of types grown in India has been made and 210 types have been described with reference to morphological and horticultural features. An attempt was made to describe them according to a prescribed schedule, in all 77 types have been described from India and 24 from other countries. Only a few among them are of commercial importance while almost all the types grown in India are selected from natural crosses, attempts have been made to breed improved types by hybridising parental types with known qualities.

Various parts of M. indica have found extensive uses in indigenous system of medicine. The stem exudates a gum resin which is sold in Indian bazars, used in dressings for cracked feet and for scabies. It is

also considered as antisyphillitic. The bark is astringent and is used in diphtheria and rheumatism. The extracts of leaves, bark, stem and unripe fruits exhibit moderate antibacterial actIVIty against 'Micrococcuss pygenes' var aureus. The occurrence of antifungal microorganisms in ripe mango has been reported. The bark of mango trees contains tannin (16-20%) and may be used for tanning purposes . The bark yields a colouring matter which produces beautiful, though light yellow shades on cotton, silk and wool in conjunction with turmeric and lime. The bark dyes cotton a bright rose-pink l

.

Chemical investigations on M. indica reported the presence of free sugars, phenolic compounds, Alono­and sesqui terpenoids in various parts (i .e.,) leaves2

-4,

fruits5, f1owers6

, bark7. The triterpenoids and steroids constituents isolated so far were recorded in Table I.

Nigam and Mitra were the first to study the triterpenoid constituents of M. indica, and thel recorded the isolation of friedelin 1 from the roots . Later, the Italians, Corsano and his co-workers9

.l5

studied in detail the triterpenoid constituents of res in, which was secured from an Indian firm and reported the isolation of eleven new triterpenoids of cycloartane skeleton besides seven known compounds. Mangiferolic acid9 2 is thet'irst example of triterpene carboxylic acid containing cyclopropane resin isolated from the risin of M. indica. Sukh-dev and Chandan Singh27 reported the partial synthesis of Mangiferolic acid 2 from cycloartenol 9.

Difference in the chemical constituents of M. indica Linn. infected with Aspergillus niger and Fusarium moniliformae was studied by S Ghosal et aP8 and reported the presence of lupenone 63, lupeol 11, ursolic acid 65 and glochidonol 64 from various parts. The isolation of novel 9,19-

884 INDIAN J CHEM. SEC B, DECEMBER 2000

I R

COOH H H

1 o COOH OH H

o COOH H H

COOH H H

, COOH OH H

, CH, H H

15 CHO H CH,

CHO H H

CH,OH H H

COOH OH H

o H H

cyclotriterpenoids from the resin of M. indica by Corsano and his Co-workers9-15 prompted to carry out phytochemical examination on various parts of M. indica for triterpenoid constituents. The leaves l6

, the root-bark 17 and the stem-bark l s of Banganpalli variety were collected at Seetanagaram near Rajahmundry, Andhra Pradesh. The chemical examination rest:lted In the isolation of known trite! enoids from leaves1u

, root-barkl 7 but the stem­barl<.i S yielded SIX new tetracyclic triterpe.noids cycloart-24-ene-31), 26-diol 25, the C-24 epimers of cycloart-25-ene-31) , 24, 27-tr'01 30, the C-24 epimers

of cycloartane-31), 24, 25-triol 31 and 3-ketodammar-24E-ene-20S, 26-<1iol 29 together with the several known compounds. The structure of new triterpenoids were elucidated by spectroscopic and chemical methods. The isolation of 3-oxo dammar-24E-ene-20 S, 26-diol 29 is the first record of new triterpenoid of dammarane skeleton from M. indica and the observation of cleavage of C-20-C-22 in it by onium cleavage has not been observed previously in the mass spectral fragmentation of dammaranes. The stem-bark of Neelum varietyl9 collected at Lakshmaneswaram, near Narasapur in Andhra Pradesh, India gave a new pentacyclic triterpenoid, hopane-ll),31), 22-triol 35 from the neutral fraction and four new tetracyclic triterpenoid carboxylic acids 36-39 and the structures of new compounds were established by spectorscopic and chemical methods. The stem-bark of Banganpalli variety yielded only three known acids but the Neelum variety yielded eight acids out of which four are new. It is noteworthy that there is great 'variation iT' tt!C triterpenoid constituents of the stem-bark of these two varieties. One of the significant variations is that several daffiJl1arane triterpenoids have been isolated from BanganpaUi variety but no dammaranes could be detected in Neelum variety. The Himayaddin variet/ I secured from Ravicharla near Nuzvid, Andhra Pradesh, India, yielded a new dammarane triterpenoid 45 and several tetracyclic & pentacyelic triterpenoids. The tetracyelic tri terpenoids belonging to cycloartane and dammarane type of skeleton. The Chittoor variet/ o collected from the same place gave both known dammaranes and cycluartanes besides four known sterols. The Suvarnareka variet/ 3 of Vetapalem, Andhra Pradesh, India, yielded only known triterpenoids.

All the fi ve varieties collected in the state of Andhra Pradesh were found to contain several triterpenoids and only one sterol, I)-sitosterol except the Chittoor variety. Similar chemical examination of Hirnsagar variet/ 2 procured from the state of west bengal showed the presence of seven sterols and several tri terpenoids including three of friedelin type but no dammarane derivative. 29-Hydroxy mangiferonic ac id 48 from this variety is the first report of a second oxygen function in the nucleus of carboxylic ac ids of the cYeloartane skeleton. The variation of triterpenoid and steroid constituents of several varieties collected from different regions of India prompted the examination of another variety of M. indica ,Sarikhas25 from West Bengal tate.Two

ANJANEYULU el af. : THE TRITERPENOIDS AND STEROIDS FROM MANGIFERA INDICA LINN 885

Table l-Triterpenoid and steroids from mangifera indica linn

SI.No. Part of the plant Major compoWlds Structure No. Ref.

~ l. Roots Friedelin (1) 8

2. Resin Mangiferolic acid (2) 9

Hydroxy mangiferonic acid (3) 10

Mangiferonic acid (4) 11 . 12

Isomangiferolic acid (5)

Hydroxy mangiferolic acid (6) 12

Ambonic acid (7) 11 . 13

Ambolic acid (8)

Cycloartenol (9) 13

24-methylene cycloartanol (10)

Lupeol (11)

a- amyrin (12)

~amyrin (13)

24 - methylene cycloartane-313. (14) 14

26- diol

24-methyl-3~ hydroxy cycloart-

24-en-26-a1 (15)

Oleanolic aldehyde (16)

Dammarenediol-Il (17) IS

Erythrodiol (18)

313 -hydroxy cycloart-24ren-26-al (19)

24-methylene-3p-hydroxy (20)

cycloartan-26-yl ambon ate

3. Leaves Friedelin (1) 16

Taraxerone (21)

Taraxerol (22)

Lupeol (11)

4. Root- bark Friedelin (1) 17

F~edelan-313-ol (23)

Cycloartenol (9)

a- amyri n (12)

13- amyrin (13)

Mangiferonic acid (4) Mangiferolic acid (2)

S. Stem-bark Cycloartenol (9) 18

(BanganpalJi variety) a- amyrin (12)

('uuld

886

SI.No.

INDIAN J CHEM, SEC B, DECEMBER 2000

Table I-Triterpenoid and steroids from mangifera indica linn- Collld

Part of the plant Major compounds Structure No.

(Neelum variety)

B-amyrin

B- sitosterol

3 B-hydrox ycycloart -24-en-26-a1

Dammarene diol - II

Cycloart-24-en-3[3, 26-diol

C-24-epimers of cycloart -

25-ene-3B,24-diol

24-methylene cycloartane-3B, 26-diol

1jI- taraxastane-3B,20-diol

, Ocotillol - II

3-oxo-dammar-24E-ene-20S, 26-diol

C-24 epimers of cycloart -

25-ene - 3B, 24, 27- triol

C-24 epimers of cycloartane-3B, 24, 25- triol

Mangiferonic acid

Mangiferolic acid

Isomangiferolic acid

Cycloartenol

a- amyrin

B- amyrin

(3- sitosterol

3(3-h ydrox ycycloartan-24-en-26-a1

C-24 epimers of cyloart-25-ene-3B,24-diol

24-methylene cycloartane-3B,26-diol

Cycloart-23-ene-313, 25-diol

Cycloartane-3(3,25-diol

Epi-ljI-taraxastane-313,20-diol

C-24 epimers of cycloartane-3f3.24.25-triol

C-24 epimers of cycloart-25-ene-313.24.27 - triol

Hopane- II3.3I3 , 22-triol

Mangiferonic acid

MangiferoJic acid

Isomangi feroli c acid

HydroxymangiferoJic acid

3a, 22 (R or S) - dihydroxy-cycloart-

24E-en-26-oic acid

3(3.22 (R or S) - dihydroxy-cycloart-

24E-en-26-oic acid

(13)

(24)

(19)

(17)

(25)

(26)

(14)

(27)

(28)

(29)

(30)

(31)

(4)

(2)

(5)

(9)

(12)

(13)

(24)

(19)

(26)

(14)

(32)

(33)

(.34)

(.31)

(30)

(35)

(4)

(2)

(5)

(11)

(36)

(37)

Ref.

19

Contd

ANJANEYULU et at.: THE TRITERPENOIDS AND STEROIDS FROM MANGIFERA INDICA LINN 887

Table l-Triterpenoid and steroids from mangifera indica Iinn-Conld

SI.No. Part of the plant Major compounds Structure No. Ref. ;.

3~, 23 (R or S) - dihydroxy-cycloart- (38)

24E-en-26-oic acid

3u, 27 (R or S) - dihydroxy-cycloart- (39)

24E-en-26-oic acid

(Chittoor Variety) Cycloartenone (40) 20

Cycloartenol (9)

~-Sitosterol (24)

C-24 epimers of cycloart-25-ene-3~,24-diol (26)

Damlnar-24-ene-3~ , 20S - diol (17)

Ocotillol - II (28)

6~ -hydroxy stigmasta-4-en-3-one (41)

6~ -hydroxy campest-4-en-3-one (42)

6~ -hydroxy stigmasta-4,22-dien-3-one (43)

3-oxo-damrnar-24-ene-20S,26-diol (29)

Mangiferonic acid (4)

Mangiferolic acid (2)

Hydroxy mangiferolic acid (11)

(BImayIIddJD variety) Cycloartenol (9) 21

u- amyrin (12)

~-amyrin (13)

13- sitosterol (24)

C-24 epimers of cycloart-25-ene-3~ ,24-diol (26)

'1/- taraxastane-3~,20-diol (27)

Taraxastane-3~ ,22-diol (44)

OcotillolII (28)

C-24 epimers of cycloartane-3~ ,24,25-triol (31)

3-oxo-damrnar-24-ene-20S, 26a- , diol (29)

3-oxo-20S, 24R-epoxy-damrnarane-25 , (45)

26 - diol

Mangiferonic acid (4)

Mangiferolic acid (2)

Isomangiferolic acid (5)

~- sitosterol (24)

~- sitosterol -3-0-~-D-glucoside (46)

(Himsagar Variety) Friedelin (1) 22

Friedelan-3~-ol (23)

Friedelan -3u-ol (47)

Conld

888 INDIAN J CHEM, SEC B, DECEMBER 2000

Table I--Triterpenoid and steroids from mangifera indica linn-Contd

SLNo. Part of the plant Major compounds Structure No. Ref.

Epi -\If -taraxastane-3 ~,20-diol (34)

C-24 epimers of cycloartane-3~,24,25-triol (31)

Mangiferonic acid (4)

Mangiferolic acid (2)

3-oxo-29-hydroxy cycloart-24E-en-26- (48)

oic acid

3a, 22 (R or S) - dihydroxy-cycloart- (36)

24E-en-26-oic acid

Hydroxymangiferolic acid (11)

~-Sitosterol archidate (49)

6~ -hydroxy stigmasta-4-en-3-one (41)

6~ -hydroxy campest-4-en-3-one (42)

6~ -hydroxy stigmasta-4,22-dien-3-one (43)

5a- stigmastane-3~, 6a-diol (50)

(Suvarnareka Cycloartenol (9) 23

variety)

~- sitosterol (24)

C-24 epimers of cycloart-25-ene-313,24-diol (26)

Cycloart -24-en-3~, 26-diol (25)

20(S)-dammar-24-ene-3~,20-diol (17)

II a, 12a- oxidotaraxerol (51)

Ocotillol - II (28)

C-24 epimers of cycloartane-3~,24,25-triol (31)

Mangiferonic acid (4) ,.

Mangiferolic acid (2)

Isomangiferolic acid (5)

Hydroxymangiferolic acid (11)

(Cultivar Chausa) Manghopanal (52) 24

Mangoleanone (53)

Friedelin (1)

C-24 epimers of cycloart - 25 - en - 3~ ,

24, 27 - triol triacetate (54)

Mangiferonic acid (4)

(Sarikhas variety) Cycloartenone (40) 25

24-melhylene cycloartanone (55)

Taraxerone (21)

Friedelan-3~ -01 (23)

Taraxerol (22)

Contd

SI.No.

ANJANEYULU et al.: THE TRITERPENOIDS AND STEROIDS FROM MANGIFERA INDICA LINN 889

Part of the plant

(Cultivar Desi)

Table. I-Triterpenoid and steroids from mangifera indica linn-Contd

Major compounds

Friedelan-3cx -01

cx- amyrin

~-amyrin

Cycloartenol

24-rnethylene cycloartanol

~- sitosterol

25 (R)-3 - oxo - 24- methylene

Cycloartan-26-01

\11- Taraxastanonol

1 1 cx, 12cx - oxidotaraxerol

6~ -hydroxy stigmasta-4-en-3-one

24-rnethylene cycloartane-3~ ,26-aiol

C-24 epimers of cycloartane-3~,24,25-triol

Mangiferonic acid

Ambonic acid

isomangiferolic acid

Mangiferolic acid

Ambolic acid

3~, 22 (R or S) - dihydroxy-cycloart-

24E-en-26-oic acid

3-oxo-23(R or S) hydroxy cycloart-24E­

en-26-oic acid

3~, 23 (R or S) - dihydroxy-cycloart-

24E-en-26-oic acid

23 - epimers of 3~ , 23-dihydroxy­

cycloart-24E-en-26-oic acid

olean - 13(18) - en - 11 - one

Urs - 3 - one

30 - desmethyl - Urs - 3 - on - 20-01

t>- sitosterol glycoside

Structure No.

(47)

(12)

(13)

(9)

(20)

(24)

(56)

(57)

(51)

(41)

(14)

(31)

(4)

(7)

(5)

(2)

(8)

(36)

(58)

(38)

(59)

(60)

(61)

(62)

(46)

Ref.

26

new neutral triterpenoids 56, 57 and three new tetracyclic carboxylicacids 38, 58, 59 have been reported from this v.wiety. The stem-bark of this variety gave eight triterpenoids containing 3-oxo group and six triterpenoids of cycloartane skeleton. Previous investigations on different varieties of M. indica afforded only one 24-methylene cycloartane derivative, 24-methylene cycloartane-3!), 26-diol 14. The isolation of several 24-methylene cycloartane triterpenoids and the co-occurrence of many pairs of

3-oxo triterpenoids and their corresponding reduced hydroxy derivative~ from Sarikhas variety is of some cheniotaxonomic significance.

Sharma and AIl24 reported two new triterpenoids namely manghopanol 52, mangoleanone 53 in addition to the known compounds Taraxerol 22 Friedelin 1, C-24 epimers of cycloart-25 ene-313, 24, 27-triol triacetate 54 and mangiferonic acid 4 from the stem-bark of Cultivar chausa collected at New Delhj.

Recently Gupta and Ali26 reported three new

890 rNDlAN J CHEM, SEC B, DECEMBER 2000

H

~ Rl

R2 Rl R2

R

Rl 0

/00 7 0 COOH (OH 17 CH)

/OH 'H 13

8 ~. COOH ""'H

"'. H 29 0 CH20H /OH

/OH 47 ~

10 ". CH 3 ""H H

14 /OH

CH2

0H .... '~H

~~ 0 CH3

1.t 0

22 /OH .... " ... , .....

H 10

24

1 46

49

ANJANEYULU et al.: THE TRlTERPENOIDS AND STEltOlDS FROM MANGIFERA INDICA LINN 891

It

R RI Rl

H 26 H H

- 13 -0 - Glucose 30 H OH

-~ (CH2 )18 - CH3 54 Ac Ac

-~OH

HO

33

" ' ~ ., .... H

35

It] 27

H

OH 34

OAc !7

HO

31

32

R

/00-''''H

OH < (C-20 epimer of27) H

0

COOl! R

/H 36 ••• ~ ••

'OH /OH

37 < '·····H

892 INDIAN] CHEM. SEC B. DECEMBER 2000

COOH R

RI

OH OH

RI Rl R

38 /00

OH (Ror S) 41 M HO """" ' H

58 0 OH (Ror S)

0 /00 42 59 OH( Rand S)

M """"'H

43

COOH

o

48

,-"" ""(

H (:m

51 52

C~OH

-"

ANJANEYULU et at.: THE TRITERPENOIDS AND STEROIDS FROM MANGIFERAlNDlCA LINN 893

60 61

62

R

o

<OH

H

"1 pentacyclic triterpenes namely Olean-13 18-en-ll­one 60, urs-3 one 61, 30-desmethyl-urs-3-on-20-ol 62 and a known compound, ~-sitosterol glycoside from the root-bark of M. indica Cultivar desi collected at Chhatarpur districts of Madhya Pradesh.

The stem-bark of M. sylvatica Roxb. collected at Andaman-Nicobar Islands yielded friedelin 1, friedelan-3~-01 23, cycloartenol 9, obtusifoldienol 66 and ~-sitosterol 24. Extensive column chromato­graphy of acidic fraction did not yield any triterpenoid carboxylic acid.

Summary The chemical examination of stem-bark of various

varieties of M. indica of Andhra Pradesh18-21

,23 and West Bengal22

,25 yielded predominantly new tetra­cyclic triterpenoids where as of North India24

,26 gave "'" new pentacyclic triterpenoids only.

Acknowledgement The authors thank CSJR, New Delhi for financial

assistance as Research Associateship (CSIR-RA) to Dr (Mrs.) P R.

References I Saslri B M, The Wealth of India: A Dictionary of Indian Raw

Materials and Industrial Products. Vol , VI, (CSIR, India), 1962, 265 and references cited therein.

2 Gabry Y ME, Osman, A M & Sheta AE, Indian J. Chem:, II , 1973, 405.

3 Sissi E, Hassan I & Saleh N A M, Planta Med. , 18, 1970, 73.

"- 4 Paris R R & Jacquemin, H. C. R. Acad. Sci. Paris, 270, 1970, 3232.

5 Anasari MAE, Reddy K K, Sharma S K N & Nayudamma Y, Leather Sci .. 16, 1969, 13.

66

6 Bose J L & Siddiqui S, J.Sci. Ind. Res (India), 7B, 1948, 100. 7 Ansari MAE, Rajadurai , S & Nayudamma Y, Leather Sci ..

14, 1967, 247. 8 Nigam S K & Mitra C R, Indian J. Chem. 1964, 378 9 Corsano S & Mincione E, Tetrahedron Lett. 1965, 2377

10 Corsano S & Piancatelli G, Rie. Sci. 35(l1-A). 1965, 484; Chem Abstr. 63, 81181C.

II Corsano S & Mincione E, Rie Sci, 36, 1966, 494; Chem Abstr. 66, 1967. 11062x.

12 Corsano S & Mincione E, Ann Chim (Rome), 57, 1967. 508; Chem Abstr. 68, 1968, 13209 d.

13 Corsano S & Mincione E, Ann Chim (Rome), 57, 1967, 522; Chem Abstr. 68, 1968. 132 1Ox.

14 Corsano S & Mincione E, Rie Sci, 37, 1967, 370; Chem Abstr. 67, 1967 116988r.

15 Mincione E, Lavarone C & Corsano S, Rie Sci. 38, 1968, 537; ChemAbstr. 70, 1969, 78191 c.

16 Anjaneyulu V, Prasad K H & Rao G S, Indian J Phann Sci. 44, 1982, 58.

17 Anjaneyulu V. Prasad K H & Rao G S, Indian J Phann Sci, 44, 1982, 85.

18 Anjaneyulu V, Prasad K H. Ravi K & Connolly D, Phytochemistry., 24, 1985. 2359.

19 Anjaneyulu V, Ravi K • . Prasad K H & Connolly J D, Phytochemistry, 28, 1989, 1471.

20 Anjaneyulu V, Suresh Babu J & Murali Krishna M. Acta Ciencia Indica, 18C, 1992, 173.

21 Anjaneyulu V, Suresh Babu J, Murali Krishna M & Connolly J D. Phytochemistry, 32, 1993. 469.

22 Anjaneyulu V, Suresh Babu J, & Connolly J D Phytochemistry, 35, 1994, 1301.

23 Anjaneyulu V, Suresh Babu J & Jyothi G, Acta Ciellcia Indica, 18C, 1992, 173.

24 Sharma S K & Ali M, Indian J Pharm Sci, 56 (2), 1994. 25 Anjaneyulu V, Satyanarayana P, Viswanatharn K N, Jyothi V

G, Nageswara Rao K & Radhika P, Phytochemistry, 50. 1999, 229.

26 Gupta J & Ali M, Indian J Chem, 38B, 1999, 1093. 27 Sukh Dev & Chandan Singh, Tetrahedron. 33, 1977. 817. 28 Ghosal S, Biswas K & Chattopadhyay B K, Phytochemistry.

17, 1978, 689.