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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
FITONE FITONE 502-69-2 C18H36O
CIMIGENOL 3-O-BETA-D-XYLOPYRANOSIDE CIMIGENOL 3-O-BETA-D-XYLOPYRANOSIDE 27994-11-2 C35H56O9
Ganodermenonol Ganodermenonol 104700-97-2 C30H46O2
ALPHA-ONOCERIN ALPHA-ONOCERIN 511-01-3 C30H50O2
ailanthone ailanthone 981-15-7 C20H24O7
artemisic acid artemisic acid 80286-58-4 C15H22O2
DESACETYLNIMBIN DESACETYLNIMBIN 18609-16-0 C28H34O8
alpha-Amyrenyl acetate alpha-Amyrenyl acetate 863-76-3 C32H52O2
(4aS,6aS,6aR,8aR,12aS,14aS,14bS)-4,4,6a,6a,8a,11,11,14b-octamethyl-2,4 a,5,6,8,9,10,12,12a,13,14,14a-dodecahydro-1H-picen-3-one (4aS,6aS,6aR,8aR,12aS,14aS,14bS)-4,4,6a,6a,8a,11,11,14b-octamethyl-2,4 a,5,6,8,9,10,12,12a,13,14,14a-dodecahydro-1H-picen-3-one 514-07-8 C30H48O
3-Oxo-olean-12-en-28-oic acid 3-Oxo-olean-12-en-28-oic acid 17990-42-0 C30H46O3
1-(4-Isopropyl-1-methyl-4-pentenyl)-3a,6,6,12a-tetramethyltetradecahyd ro-1H-cyclopenta[a]cyclopropa[e]phenanthren-7-yl acetate 1-(4-Isopropyl-1-methyl-4-pentenyl)-3a,6,6,12a-tetramethyltetradecahyd ro-1H-cyclopenta[a]cyclopropa[e]phenanthren-7-yl acetate 1259-94-5 C33H54O2
[(3S,4aS,6aR,6bS,8aR,12aR,14aS,14bS)-4,4,6a,6b,8a,11,11,14b-octamethyl -1,2,3,4a,5,6,7,8,9,10,12,12a,14,14a-tetradecahydropicen-3-yl] acetate [(3S,4aS,6aR,6bS,8aR,12aR,14aS,14bS)-4,4,6a,6b,8a,11,11,14b-octamethyl -1,2,3,4a,5,6,7,8,9,10,12,12a,14,14a-tetradecahydropicen-3-yl] acetate 1616-93-9 C32H52O2
6β,16-Dihydroxykauran-2β-yl β-D-glucopyranoside 6β,16-Dihydroxykauran-2β-yl β-D-glucopyranoside 53452-34-9 C26H44O8
Rutundic acid Rutundic acid 20137-37-5 C30H48O5
4-Hydroxy-2,6,6-trimethyl-1-cyclohexenecarboxylic acid 4-Hydroxy-2,6,6-trimethyl-1-cyclohexenecarboxylic acid 62218-55-7 C10H16O3
(13α,14β,17α,20S,23R,24S)-21,24-Epoxy-23,25-dihydroxy-5α-lanost-7-en-3-one (13α,14β,17α,20S,23R,24S)-21,24-Epoxy-23,25-dihydroxy-5α-lanost-7-en-3-one 6985-35-9 C30H48O4
D:B-Friedo-B':A'-neogammacer-5-en-3β-ol D:B-Friedo-B':A'-neogammacer-5-en-3β-ol 1615-94-7 C30H50O
13-Hydroxy-8,11,13-podocarpatrien-18-oic acid 13-Hydroxy-8,11,13-podocarpatrien-18-oic acid 61597-83-9 C17H22O3
2α,3α,24-Trihydroxyurs-12-en-28-oic acid 2α,3α,24-Trihydroxyurs-12-en-28-oic acid 89786-83-4 C30H48O5
Gadermandiol Gadermandiol 107900-76-5 C30H48O3
PIMARIC ACID PIMARIC ACID 127-27-5 C20H30O2
WILFORGINE WILFORGINE 37239-47-7 C41H47NO19
28-deoxonimbolide 28-deoxonimbolide 126005-94-5 C27H32O6
rosenonolactone rosenonolactone 508-71-4 C20H28O3
xanthatin xanthatin 26791-73-1 C15H18O3
3-Epikatonic acid 3-Epikatonic acid 76035-62-6 C30H48O3
Phytolaccagenin Phytolaccagenin 1802-12-6 C31H48O7
(23S)-17,23-Epoxy-29-hydroxy-27-nor-5α-lanost-8-ene-3,24-dione (23S)-17,23-Epoxy-29-hydroxy-27-nor-5α-lanost-8-ene-3,24-dione 81678-46-8 C29H44O4
Hop-17(21)-en-3β-ol Hop-17(21)-en-3β-ol 564-14-7 C30H50O
3-Methyl-2-butenoic acid [2-[5-hydroxy-2-methyl-2-(4-methyl-3-pentenyl)-6-oxo-7-(2-oxopropyl)-4-cyclohepten-1-yl]vinyl] ester 3-Methyl-2-butenoic acid [2-[5-hydroxy-2-methyl-2-(4-methyl-3-pentenyl)-6-oxo-7-(2-oxopropyl)-4-cyclohepten-1-yl]vinyl] ester 74690-89-4 C25H36O5
(4aR)-5β-[2-(3-Furyl)ethyl]-3,4,4aβ,5,6,7,8,8a-octahydro-5,6α,8aα-trimethyl-1-naphthalenecarboxylic acid (4aR)-5β-[2-(3-Furyl)ethyl]-3,4,4aβ,5,6,7,8,8a-octahydro-5,6α,8aα-trimethyl-1-naphthalenecarboxylic acid 1782-65-6 C20H28O3
12-Hydroxy-8(17),13-labdadien-16,15-olide 12-Hydroxy-8(17),13-labdadien-16,15-olide 958885-86-4 C20H30O3
15,18-Dihydroxyabieta-8,11,13-trien-7-one 15,18-Dihydroxyabieta-8,11,13-trien-7-one 213329-45-4 C20H28O3
20,24-Epoxy-24-methoxy-23(24-25)abeo-dammaran-3-one 20,24-Epoxy-24-methoxy-23(24-25)abeo-dammaran-3-one 1020074-97-8 C31H52O3
3-Acetoxy-27-hydroxy-20(29)-lupen
-28-oic acid methyl ester 3-Acetoxy-27-hydroxy-20(29)-lupen -28-oic acid methyl ester 263844-80-0 C33H52O5
3-O-Acetyloleanderolide 3-O-Acetyloleanderolide 62498-83-3 C32H50O5
Cabraleahydroxylactone Cabraleahydroxylactone 35833-69-3 C27H44O3
Celaphal A Celaphal A 244204-40-8 C17H20O4
Coronarin D ethyl ether Coronarin D ethyl ether 138965-89-6 C22H34O3
Echiphyllin C Echiphyllin C 310433-44-4 C20H29NO3
ent-14,16-Epoxy-8-pimarene-3,15-diol ent-14,16-Epoxy-8-pimarene-3,15-diol 1188281-98-2 C20H32O3
Eriocalyxin B Eriocalyxin B 84745-95-9 C20H24O5
Hythiemoside A Hythiemoside A 853267-91-1 C28H46O9
Methyl eichlerianate Methyl eichlerianate 56421-12-6 C31H52O4
Myriceric acid B Myriceric acid B 55497-79-5 C39H54O7
Pre-schisanartanin B Pre-schisanartanin B 1033288-92-4 C31H42O11
SOYASAPOGENOL B(P) SOYASAPOGENOL B(P) 595-15-3 C30H50O3
grandifloric acid grandifloric acid 22338-69-8 C20H30O3
moronic acid moronic acid 6713-27-5 C30H46O3
actinidic acid actinidic acid 341971-45-7 C30H46O5
taxinine M taxinine M 135730-55-1 C35H42O14
steviolbioside steviolbioside 41093-60-1 C32H50O13
Carabrone Carabrone 1748-81-8 C15H20O3
10-DEACETYL-7-XYLOSYLPACLITAXEL 10-DEACETYL-7-XYLOSYLPACLITAXEL 90332-65-3 C49H63NO17
Arteannuin Arteannuin 50906-56-4 C15H20O3
isocupressic acid isocupressic acid 1909-91-7 C20H32O3
taraxerol taraxerol 127-22-0 C30H50O
D-Friedoolean-14-ene-3β,28-diol D-Friedoolean-14-ene-3β,28-diol 17884-88-7 C30H50O2
(1R,8S)-1α-(3-Furanyl)-6,7,8,9-tetrahydro-8α-[(2,5-dihydro-2-oxofuran)-3-yl]naphtho[1,2-c]furan-3(1H)-one (1R,8S)-1α-(3-Furanyl)-6,7,8,9-tetrahydro-8α-[(2,5-dihydro-2-oxofuran)-3-yl]naphtho[1,2-c]furan-3(1H)-one 126724-95-6 C20H16O5
16-Kaurene-2,6,15-triol 16-Kaurene-2,6,15-triol 53452-32-7 C20H32O3
6-Deoxy-9alpha-hydroxycedrodorin 6-Deoxy-9alpha-hydroxycedrodorin 247036-52-8 C27H34O9
Dihydroniloticin Dihydroniloticin 115334-05-9 C30H50O3
ent-9-Hydroxy-15-oxo-16-kauren-
19-oic acid beta-D-glucopyrasyl ester ent-9-Hydroxy-15-oxo-16-kauren- 19-oic acid beta-D-glucopyrasyl ester 81263-96-9 C26H38O9
Eucamalol Eucamalol 145544-91-8 C10H16O2
Itol A Itol A 1033747-78-2 C20H32O6
Micraic acid A Micraic acid A 659738-08-6 C22H32O3
Olean-12-ene-3,24-diol Olean-12-ene-3,24-diol 119318-15-9 C30H50O2
Pseudolaric acid D Pseudolaric acid D 115028-67-6 C20H30O3
Scutellaric acid Scutellaric acid 102919-76-6 C30H48O4
Wilforol C Wilforol C 168254-95-3 C30H48O4
3,4-Secocucurbita-4,24-diene-3,26,29-trioic acid 3,4-Secocucurbita-4,24-diene-3,26,29-trioic acid 329975-47-5 C30H46O6
(24S)-Cycloartane-3,24,25-triol 24,25-acetonide (24S)-Cycloartane-3,24,25-triol 24,25-acetonide 57576-31-5 C33H56O3
14-Deoxy-11-hydroxyandrographolide 14-Deoxy-11-hydroxyandrographolide 160242-09-1 C20H30O5
2-Oxokolavelool 2-Oxokolavelool 221466-41-7 C20H32O2
3,19-Dihydroxy-6,23-dioxo-12-ursen-28-oic acid 3,19-Dihydroxy-6,23-dioxo-12-ursen-28-oic acid 261768-88-1 C30H44O6
CaMaric acid CaMaric acid 146450-83-1 C35H52O6
PoMolic acid 28-O-beta-D-glucopyranosyl ester PoMolic acid 28-O-beta-D-glucopyranosyl ester 83725-24-0 C36H58O9
Scutebarbatine X Scutebarbatine X 1312716-26-9 C34H38N2O10
Uncinatone Uncinatone 99624-92-7 C20H22O4
β-AMyrenonol acetate β-AMyrenonol acetate 5356-56-9 C32H50O3
DACRENE DACRENE 20070-61-5 C20H32
(2S)-2β-(3-Furyl)-4aα,5,6aβ,7,10,11,11aα,11b-octahydro-11bβ-methyl-7β,10β-methano-2H-pyrano[4,3-g][3]benzoxepine-4,6,8(1H)-trione (2S)-2β-(3-Furyl)-4aα,5,6aβ,7,10,11,11aα,11b-octahydro-11bβ-methyl-7β,10β-methano-2H-pyrano[4,3-g][3]benzoxepine-4,6,8(1H)-trione 66756-57-8 C19H20O6
Rosthornin B Rosthornin B 125181-21-7 C24H34O7
Tereticornate A Tereticornate A 149751-81-5 C40H54O6
Villosin Villosin 160598-92-5 C20H28O2
2,5,14-Triacetoxy-3-benzoyloxy-8,15-dihydroxy-7-isobutyroyloxy-9-nicotinoyloxyjatropha-6(17),11E-diene 2,5,14-Triacetoxy-3-benzoyloxy-8,15-dihydroxy-7-isobutyroyloxy-9-nicotinoyloxyjatropha-6(17),11E-diene 210108-87-5 C43H53NO14
Andropanolide Andropanolide 869807-57-8 C20H30O5
GANODERIC ACID DM GANODERIC ACID DM 173075-45-1 C30H44O4
(13E)-15-Hydroxy-8(17),13-labdadiene-19-al (13E)-15-Hydroxy-8(17),13-labdadiene-19-al 3650-31-5 C20H32O2
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
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