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Terpenes

Terpenes is the generic term summarizing all kinds of isoprene polymers and their derivatives with its general formula of (C5H8) n. Terpene is a class of compound that is ubiquitous in the plant kingdom, but exist in very few amount in the animal kingdom. Except in the form of terpene hydrocarbons, there are a large number of terpenes forming various kinds of oxygenated derivatives including alcohols, aldehydes, ketones, carboxylic acids, esters and glycoside forms. Secondly there are also nitrogen-containing derivatives as well as a minority of sulfur-containing derivatives presented. Based on the number of the isoprene units contained inside the molecule, the terpenes can be divided into: monoterpene, sesquiterpenoid, diterpene, sesquiterpene, triterpenoids, tetraterpene and polyterpene.

For some compound which originated from the synthesis of isoprene, but has the number of carbon atoms in the molecule be not an integer multiple of 5, they are called terpenoid. In the life activities, terpenoids compound, especially inside the plants, have important functions, for example gibberellin, abscisic acid and insect juvenile hormone are important hormones, carotenoids and chlorophyll are important photosynthetic pigments; plastoquinone and quinone are respectively important electronic chain delivery body in photosynthesis and respiration chain; sterols are the component of the biological membrane.

Monoterpene and sesquiterpene are the major component of volatile oil. Diterpene is the major substance forming the resin; triterpenoid is an important material forming plant saponins and resins, tetraterpene mainly include some fat-soluble pigments widely distributed in the plants. In nature, terpenoids is widely distributed, some of which have physiological activity. For example, ascaridole and santonin have roundworm expelling effect; artemisinin has antimalarial effect while andrographolidume has antibacterial effect.

The following describes some of the chemical reactions associated with terpenes. This is significant for determination of the chemical structure of terpene component.

(1) Oxidation reaction
Different oxidants, in different situations, can oxidize the different groups contained in terpene component to produce different products. For example, chromic acid can oxidize the carbon methyl group and gem-dimethyl carbon to produce acetic acid; the oxidation reaction of ozone is a valuable double bond cleavage reaction and can determine the position of double bond in the structure of the terpene composition. Lead tetraacetate is also oxidation agents of double-bond and has been widely used in chemical research of the terpene ingredients.

(2) The dehydrogenation
Dehydrogenation reaction can be considered as a kind of oxidation reactions and is a kind of valuable reaction for the study the chemical structure of terpenes particularly cyclic terpene. It refers to that the terpene component is heated (200 ℃ ~ 300 ℃) together with sulfur or selenium under an inert atmosphere, the carbon skeleton of the cyclic terpene is dehydrogenated into aromatic derivatives with sometimes the ring being cleaved and sometimes cyclization occurring simultaneously.

(3) Addition reaction
The double bonds in the terpene components can react with hydrogen halide acids such as hydroiodic acid or hydrogen chloride in glacial acetic acid solution to generate crystalline-shaped addition product. It can also absorb bromine (diethyl ether or glacial acetic acid - ethanol solution) to generate bromide with certain physicochemical properties. If mixing the glacial acetic acid and sodium nitrite for shaking, nitrous oxide or pseudo-nitrous oxide will be generate and will exhibit visible special colors.
If the unsaturated terpene component was added with amyl nitrite and concentrated hydrochloric acid for mixing with shaking and keep it cool, then add a small amount of ethanol or glacial acetic acid, there will be chlorinated nitroso derivative of terpenes generated with special colors as well. Such nitroso derivatives (including nitrous oxides and chlorinated nitroso derivative) mostly exhibit blue or blue-green color. They are easily polymerized to form a colorless di-polymer, but when the di-polymer is heated to a molten state or when made into a solution, it can also be converted into a blue or blue-green single-molecule compound.
Nitroso chlorinated derivatives can condense with primary or secondary amines (commonly piperidine) to generate nitroso amines with most of them having complete crystal shape and  certain physical and chemical constants available for the identification of unsaturated terpene components. If the terpene component molecules contain conjugated double bonds, then it will form crystalline addition product with maleic anhydride through Diels-Alder reaction which can be used to prove the presence of conjugated double bonds.

(4) Wagner-Meerweein rearrangement;
Terpene molecules, sometimes through the effect of agents (such as acid, etc.), the carbon skeleton can be changed or the functional groups in the molecule can be transferred in the molecule. Especially during the elimination reaction, addition reaction or a nucleophilic substitution reaction of bicyclic terpene compound, there is often Wagner-Meerweein rearrangement happening.

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Structure Chemical Name CAS MF
Isotschimgin Isotschimgin 62356-47-2 C17H22O3
Liangshanin A Liangshanin A 122717-54-8 C20H26O4
Masticadielic acid Masticadielic acid 472-30-0 C30H48O3
Methylpseudolarate B Methylpseudolarate B 82508-34-7 C24H30O8
Momethyl kolavate Momethyl kolavate 24513-41-5 C21H32O4
Simiarene Simiarene 2318-78-7 C30H48O
Tetrahydroxysqualene Tetrahydroxysqualene 1043629-23-7 C30H50O4
15,16-Dihydro-15-Methoxy-16-oxohardwickiic acid 15,16-Dihydro-15-Methoxy-16-oxohardwickiic acid 115783-35-2 C21H30O5
3,27-Dihydroxy-20(29)-lupen-28-oic acid Methyl ester 3,27-Dihydroxy-20(29)-lupen-28-oic acid Methyl ester 263844-79-7 C31H50O4
14-Deoxy-11,12-didehydroandrographiside 14-Deoxy-11,12-didehydroandrographiside 141973-41-3 C26H38O9
3,10-Dihydroxy-5,11-dielMenthadiene-4,9-dione 3,10-Dihydroxy-5,11-dielMenthadiene-4,9-dione 106623-23-8 C20H28O4
Ohchinin acetate Ohchinin acetate 67023-81-8 C38H44O9
Quinovic acid 3-O-alpha-L-rhaMnopyranoside Quinovic acid 3-O-alpha-L-rhaMnopyranoside 104055-76-7 C36H56O9
ZEORINE ZEORINE 22570-53-2 C30H52O2
Trichokaurin Trichokaurin 23811-50-9 C24H34O7
Daturabietatriene Daturabietatriene 65894-41-9 C20H30O2
Dihydroajugapitin Dihydroajugapitin 87480-84-0 C29H44O10
(24Z)-3,4-Secolanosta-4(28),9(11),24-triene-3,26-dioic acid (24Z)-3,4-Secolanosta-4(28),9(11),24-triene-3,26-dioic acid 62393-88-8 C30H46O4
11α-Acetoxy-7α,20-epoxy-6β,7-dihydroxykaur-16-en-15-one 11α-Acetoxy-7α,20-epoxy-6β,7-dihydroxykaur-16-en-15-one 77949-42-9 C22H30O6
(13S)-10-Demethyl-9α-methylpimarane-5α,15,16-triol (13S)-10-Demethyl-9α-methylpimarane-5α,15,16-triol 7121-99-5 C20H36O3
13-Methyl-8,11,13-podocarpatriene-3,12-diol 13-Methyl-8,11,13-podocarpatriene-3,12-diol 769140-74-1 C18H26O2
1-O-Deacetyl-2alpha-hydroxykhayalide E 1-O-Deacetyl-2alpha-hydroxykhayalide E 1189801-51-1 C27H32O11
2,16,19-Kauranetriol 2-O-beta-D-allopyraside 2,16,19-Kauranetriol 2-O-beta-D-allopyraside 195723-38-7 C26H44O8
2,6,16-Kauranetriol 2-O-beta-D-allopyraside 2,6,16-Kauranetriol 2-O-beta-D-allopyraside 195735-16-1 C26H44O8
24,25-Dihydroxydammar-20-en-3-one 24,25-Dihydroxydammar-20-en-3-one 63543-53-3 C30H50O3
3-Hydroxy-12-oleanene-23,28-dioic acid 3-Hydroxy-12-oleanene-23,28-dioic acid 226562-47-6 C30H46O5
Abiesadine I Abiesadine I 1210347-50-4 C24H34O5
Agathadiol diacetate Agathadiol diacetate 24022-13-7 C24H38O4
Deacetylpseudolaric acid A Deacetylpseudolaric acid A 82508-37-0 C20H26O5
ent-6,11-Dihydroxy-15-oxo-16-kauren
-19-oic acid beta-D-glucopyrasyl ester ent-6,11-Dihydroxy-15-oxo-16-kauren -19-oic acid beta-D-glucopyrasyl ester 81263-97-0 C26H38O10
Erythrodiol 3-palmitate Erythrodiol 3-palmitate 19833-13-7 C46H80O3
Kamebanin Kamebanin 39388-57-3 C20H30O4
Sorghumol acetate Sorghumol acetate 90582-47-1 C32H52O2
Tanshinlactone Tanshinlactone 105351-70-0 C17H12O3
Uncargenin C Uncargenin C 152243-70-4 C30H48O5
Zamanic acid Zamanic acid 260393-05-3 C39H54O6
14-Deoxy-17-hydroxyandrographolide 14-Deoxy-17-hydroxyandrographolide 869384-82-7 C20H32O5
4-EpicoMMunic acid 4-EpicoMMunic acid 83945-57-7 C20H30O2
Ursonic acid Ursonic acid 6246-46-4 C30H46O3
(1alpha,4alpha,6alpha)-(±)-1,3,3-trimethyl-2-oxabicyclo[2.2.2]octan-6-ol (1alpha,4alpha,6alpha)-(±)-1,3,3-trimethyl-2-oxabicyclo[2.2.2]octan-6-ol 60761-00-4 C10H18O2
(4aS,10aS)-6-hydroxy-1,1,4a-trimethyl-7-propan-2-yl-3,4,10,10a-tetrahy dro-2H-phenanthren-9-one (4aS,10aS)-6-hydroxy-1,1,4a-trimethyl-7-propan-2-yl-3,4,10,10a-tetrahy dro-2H-phenanthren-9-one 511-05-7 C20H28O2
nagilactone C nagilactone C 24338-53-2 C19H22O7
rehmannic acid rehmannic acid 467-81-2 C35H52O5
psi-taraxasterol psi-taraxasterol 464-98-2 C30H50O
3α,20-Dihydroxy-4,4,14-trimethyl-18-nor-5α-cholan-24-oic acid γ-lactone 3α,20-Dihydroxy-4,4,14-trimethyl-18-nor-5α-cholan-24-oic acid γ-lactone 35833-72-8 C27H44O3
(24R)-20,24-Epoxy-25-hydroxy-3,4-seco-5α-dammar-4(28)-en-3-oic acid (24R)-20,24-Epoxy-25-hydroxy-3,4-seco-5α-dammar-4(28)-en-3-oic acid 21671-00-1 C30H50O4
(13S,14S,17S)-3,6-Dioxo-16β-hydroxylanosta-7,24-diene-21-oic acid γ-lactone (13S,14S,17S)-3,6-Dioxo-16β-hydroxylanosta-7,24-diene-21-oic acid γ-lactone 64929-59-5 C30H42O4
1,2,3,19-Tetrahydroxy-12-ursen-28-oic acid 1,2,3,19-Tetrahydroxy-12-ursen-28-oic acid 113558-03-5 C30H48O6
11,15-Dihydroxy-16-kauren-19-oic acid 11,15-Dihydroxy-16-kauren-19-oic acid 57719-76-3 C20H30O4
13-O-Deacetyltaxumairol Z 13-O-Deacetyltaxumairol Z 220935-39-7 C31H40O12
16-Hydroxy-8(17),13-
labdadien-15,16-olid-19-oic acid 16-Hydroxy-8(17),13- labdadien-15,16-olid-19-oic acid 691009-85-5 C20H28O4
22-Hydroxy-3-oxo-12-ursen-30-oic acid 22-Hydroxy-3-oxo-12-ursen-30-oic acid 173991-81-6 C30H46O4
Alstonic acid B Alstonic acid B 1159579-45-9 C30H46O3
Coronalolic acid Coronalolic acid 268214-52-4 C30H46O4
POMOLIC ACID POMOLIC ACID 13849-91-7 C30H48O4
lupeol caffeate lupeol caffeate 103917-26-6 C39H58O4
rubelloside B rubelloside B 167875-39-0 C42H66O14
pinusolide pinusolide 31685-80-0 C21H30O4
PICRASIN-B PICRASIN-B 26121-56-2 C21H28O6
1-Naphthalenepropanol,.alp 1-Naphthalenepropanol,.alp 1438-62-6 C20H34O
Baccatin VI Baccatin VI 57672-79-4 C37H46O14
Lup-20(29)-ene-1β,3β-diol Lup-20(29)-ene-1β,3β-diol 29028-10-2 C30H50O2
(20S,24S)-20,24-Epoxydammarane-3β,25-diol (20S,24S)-20,24-Epoxydammarane-3β,25-diol 19942-04-2 C30H52O3
14-Isopropylpodocarpa-8,11,13-triene-3β,13-diol 14-Isopropylpodocarpa-8,11,13-triene-3β,13-diol 3772-56-3 C20H30O2
(4S)-4α-[(Z)-2-(3-Furyl)vinyl]-4a,5,6,7,8,8aβ-hexahydro-3,4aα,8,8-tetramethylnaphthalen-1(4H)-one (4S)-4α-[(Z)-2-(3-Furyl)vinyl]-4a,5,6,7,8,8aβ-hexahydro-3,4aα,8,8-tetramethylnaphthalen-1(4H)-one 56324-54-0 C20H26O2
(1S)-2α,5α-(Epoxymethano)-1-hydroxymethyl-2-(2-hydroxyethyl)cyclopentan-1β-ol (1S)-2α,5α-(Epoxymethano)-1-hydroxymethyl-2-(2-hydroxyethyl)cyclopentan-1β-ol 126594-66-9 C9H16O4
α-Amyrenone α-Amyrenone 20248-08-2 C30H48O
3β-Acetoxy-13-hydroxyurs-11-ene-28-oic acid lactone 3β-Acetoxy-13-hydroxyurs-11-ene-28-oic acid lactone 35959-08-1 C32H48O4
3-Deoxyryanodol 3-Deoxyryanodol 62394-04-1 C20H32O7
(24E)-3-Oxo-5α-lanosta-7,9(11),24-triene-26-al (24E)-3-Oxo-5α-lanosta-7,9(11),24-triene-26-al 104700-98-3 C30H44O2
8(17),12,14-Labdatriene-19-oic acid 8(17),12,14-Labdatriene-19-oic acid 2761-77-5 C20H30O2
(13E)-15-Hydroxy-8(17),13-labdadiene-19-al (13E)-15-Hydroxy-8(17),13-labdadiene-19-al 3650-31-5 C20H32O2
Glutina-5-ene-3β-ol Glutina-5-ene-3β-ol 545-24-4 C30H50O
(23R,24S)-23,24-Dihydroxy-25-methoxy-5α-tirucall-7-en-3-one (23R,24S)-23,24-Dihydroxy-25-methoxy-5α-tirucall-7-en-3-one 115334-04-8 C31H52O4
3β,22α-Dihydroxyolean-12-en-29-oic acid 3β,22α-Dihydroxyolean-12-en-29-oic acid 84108-17-8 C30H48O4
10,13-Dideoxy-10α,21-epoxy-5β-hydroxyenmein 10,13-Dideoxy-10α,21-epoxy-5β-hydroxyenmein 85287-60-1 C20H24O6
16-O-Acetyldarutigel 16-O-Acetyldarutigel 1188282-01-0 C22H36O4
2,6,16-Kauranetriol 2,6,16-Kauranetriol 41530-90-9 C20H34O3
23-deoxojessic acid 23-deoxojessic acid 215609-93-1 C31H50O4
3-Hydroxy-11-ursen-28,13-olide 3-Hydroxy-11-ursen-28,13-olide 35959-05-8 C30H46O3
6-Epidemethylesquirolin D 6-Epidemethylesquirolin D 165074-00-0 C20H28O5
Bauerel acetate Bauerel acetate 17020-04-1 C32H52O2
Clerodermic acid methyl ester Clerodermic acid methyl ester 67650-47-9 C21H30O4
Cycloartane-3,24,25-triol Cycloartane-3,24,25-triol 57576-29-1 C30H52O3
Diosbulbin J Diosbulbin J 1187951-06-9 C19H22O8
ent-3-Oxokauran-17-oic acid ent-3-Oxokauran-17-oic acid 151561-88-5 C20H30O3
ent-9-Hydroxy-15-oxo-19-kauraic acid ent-9-Hydroxy-15-oxo-19-kauraic acid 77658-45-8 C20H30O4
Glaucin B Glaucin B 115458-73-6 C28H32O10
Heudelotine Heudelotine 133453-58-4 C18H20O2
Jangomolide Jangomolide 93767-25-0 C26H28O8
Limonexic acid Limonexic acid 99026-99-0 C26H30O10
Momordicoside G Momordicoside G 81371-54-2 C37H60O8
Pyrocincholic acid methyl ester Pyrocincholic acid methyl ester 107160-24-7 C30H48O3
Rosthornin A Rosthornin A 125164-55-8 C22H32O5
Sorghumol Sorghumol 90582-44-8 C30H50O
Quinovic acid 3-O-(6-deoxy-beta-D-glucopyranoside) 28-O-beta-D-glucopyranosyl ester Quinovic acid 3-O-(6-deoxy-beta-D-glucopyranoside) 28-O-beta-D-glucopyranosyl ester 124727-10-2 C42H66O14
2-Oxokolavenol 2-Oxokolavenol 130395-82-3 C20H32O2
3,22-Dihydroxyolean-12-en-29-oic acid 3,22-Dihydroxyolean-12-en-29-oic acid 808769-54-2 C30H48O4
(24S)-20,24-Epoxy-25-hydroxy-5α-dammaran-3-one (24S)-20,24-Epoxy-25-hydroxy-5α-dammaran-3-one 35761-54-7 C30H50O3
1β-Hydroxylup-20(29)-en-3-one 1β-Hydroxylup-20(29)-en-3-one 23963-54-4 C30H48O2
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