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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
7-epi-10-Deacetyl CephaloMannine 7-epi-10-Deacetyl CephaloMannine 78479-12-6 C43H51NO13
20-Deoxocarnosol 20-Deoxocarnosol 94529-97-2 C20H28O3
Lucidadiol Lucidadiol 252351-95-4 C30H48O3
Rubiprasin B Rubiprasin B 125263-66-3 C32H52O4
Triptonodiol Triptonodiol 117456-87-8 C21H30O4
Secaubrytriol Secaubrytriol 925932-10-1 C30H50O5
p-Menth-1-ene-3,6-diol p-Menth-1-ene-3,6-diol 4031-55-4 C10H18O2
Rediocide C Rediocide C 677277-98-4 C46H54O13
Dodonolide Dodonolide 349534-73-2 C20H24O3
LaxiraceMosin H LaxiraceMosin H 1241871-28-2 C26H35NO3
Wilforlide A acetate Wilforlide A acetate 84104-80-3 C32H48O4
5,8,9,10,14-Pentaacetoxy-3-benzoyloxy-15-hydroxypepluane 5,8,9,10,14-Pentaacetoxy-3-benzoyloxy-15-hydroxypepluane 210108-91-1 C37H48O13
cimiside B cimiside B 152685-91-1 C40H64O13
CYCLOARTANOL CYCLOARTANOL 4657-58-3 C30H52O
13-OXOPODOCARP-8(14)-EN-18-OICACID 13-OXOPODOCARP-8(14)-EN-18-OICACID 63976-69-2 C17H24O3
7-Oxodehydroabietil 7-Oxodehydroabietil 33980-71-1 C20H28O2
18-rabieta-8,11,13-trien-4-ol 18-rabieta-8,11,13-trien-4-ol 22478-65-5 C19H28O
Karavilagenin A Karavilagenin A 912329-03-4 C32H54O3
lupenyl palmitate lupenyl palmitate 32214-80-5 C46H80O2
enmein enmein 3776-39-4 C20H26O6
kolavenol kolavenol 19941-83-4 C20H34O
2-Deacetoxytaxinine B 2-Deacetoxytaxinine B 191547-12-3 C35H42O9
Deoxyelephantopin Deoxyelephantopin 29307-03-7 C19H20O6
Galeopsin Galeopsin 76475-16-6 C22H32O5
15,16-Dir-8(17),11-labdadien-13-one 15,16-Dir-8(17),11-labdadien-13-one 76497-69-3 C18H28O
19-r-4-hydroxyabieta-8,11,13-trien-7-one 19-r-4-hydroxyabieta-8,11,13-trien-7-one 57906-31-7 C19H26O2
2-Caren-10-ol 2-Caren-10-ol 6909-19-9 C10H16O
3alpha-Akeboic acid 3alpha-Akeboic acid 104777-61-9 C29H44O3
8(17),13-Labdadien-15,16-olide 8(17),13-Labdadien-15,16-olide 83324-51-0 C20H30O2
9-Hydroxy-13E-labden-15-oic acid 9-Hydroxy-13E-labden-15-oic acid 132915-47-0 C20H34O3
ent-14,15-Dir-13-oxolabda-8(17),11-dien-18-oic acid ent-14,15-Dir-13-oxolabda-8(17),11-dien-18-oic acid 875585-30-1 C18H26O3
Methyl pseudolarate A Methyl pseudolarate A 82508-33-6 C23H30O6
15,16-Epoxy-12S-hydroxylabda-8(17),13(16),14-triene 15,16-Epoxy-12S-hydroxylabda-8(17),13(16),14-triene 216011-55-1 C20H30O2
29-Norcycloart-23-ene-3,25-diol 29-Norcycloart-23-ene-3,25-diol 115040-04-5 C29H48O2
DeacetylniMbinene DeacetylniMbinene 78916-55-9 C11H8ClN3OS2
ent-17-Hydroxykaur-15-en-19-oic acid ent-17-Hydroxykaur-15-en-19-oic acid 35030-38-7 C20H30O3
Ohchinin Ohchinin 67023-80-7 C36H42O8
Trigonosin F Trigonosin F 1262842-73-8 C46H54O13
21,23:24,25-Diepoxy-21,23-
diMethoxytirucall-7-en-3-one 21,23:24,25-Diepoxy-21,23- diMethoxytirucall-7-en-3-one 1351617-74-7 C32H50O5
24(31)-Dehydrocarboxyacetylquercinic acid 24(31)-Dehydrocarboxyacetylquercinic acid 127970-62-1 C34H50O7
Pterisolic acid A Pterisolic acid A 1401419-85-9 C20H26O5
GeloMulide A GeloMulide A 122537-59-1 C22H30O5
ent-11β-Hydroxyatis-16-ene-3,14-dione ent-11β-Hydroxyatis-16-ene-3,14-dione 1092103-22-4 C20H28O3
ent-16-Kaurene-3β,15β,18-triol ent-16-Kaurene-3β,15β,18-triol 921211-29-2 C20H32O3
Danshenol C Danshenol C 910856-25-6 C21H20O4
Antiquorin Antiquorin 125356-08-3 C20H28O3
7-Xylosyl-10-deacetylbaccatin III 7-Xylosyl-10-deacetylbaccatin III 157664-03-4 C34H44O14
Bonducellpin C Bonducellpin C 197781-84-3 C23H32O7
ent-Labda-8(17),13E-diene-3β,15,18-triol ent-Labda-8(17),13E-diene-3β,15,18-triol 90851-50-6 C20H34O3
(1S,3R,6S,8R,9S,10E,12S,14S)-6,9,14-Tris(acetyloxy)-3,12-dihydroxy-1,5,16,16-tetramethyltricyclo[9.3.1.14,8]hexadeca-4,10-dien-2-one (1S,3R,6S,8R,9S,10E,12S,14S)-6,9,14-Tris(acetyloxy)-3,12-dihydroxy-1,5,16,16-tetramethyltricyclo[9.3.1.14,8]hexadeca-4,10-dien-2-one 181309-92-2 C26H36O9
9alpha,10beta,13alpha-Triacetoxy-5alpha-cinnamoyloxytaxa-4(20),11-diene 9alpha,10beta,13alpha-Triacetoxy-5alpha-cinnamoyloxytaxa-4(20),11-diene 115810-14-5 C35H44O8
Kongensin A Kongensin A 885315-96-8 C22H30O5
Methyl 7,15-dihydroxydehydroabietate Methyl 7,15-dihydroxydehydroabietate 155205-65-5 C21H30O4
Sculponeatin K Sculponeatin K 477529-70-7 C20H26O5
11α-Hydroxyobacunoic acid 3,4-lactone 11α-Hydroxyobacunoic acid 3,4-lactone 23885-43-0 C26H30O8
Lup-20(29)-ene-3α,23-diol Lup-20(29)-ene-3α,23-diol 32451-85-7 C30H50O2
Melilotigenin B Melilotigenin B 91269-84-0 C30H46O3
14beta-Benzoyloxy-2-deacetylbaccatin VI 14beta-Benzoyloxy-2-deacetylbaccatin VI 705973-69-9 C37H46O15
18-rabieta-8,11,13-triene-4,15-diol 18-rabieta-8,11,13-triene-4,15-diol 203455-81-6 C19H28O2
9,13-Epidioxy-8(14)-abieten-18-oic acid 9,13-Epidioxy-8(14)-abieten-18-oic acid 5309-35-3 C20H30O4
Abieta-8,11,13-triene-7,15,18-triol Abieta-8,11,13-triene-7,15,18-triol 337527-10-3 C20H30O3
Epieriocalyxin A Epieriocalyxin A 191545-24-1 C20H24O5
Karavilagenin D Karavilagenin D 934739-29-4 C30H46O4
Serratenediol diacetate Serratenediol diacetate 27832-84-4 C34H54O4
3-EpiMeliasenin B 3-EpiMeliasenin B 1222475-77-5 C30H44O4
Bisandrographolide C Bisandrographolide C 160498-02-2 C40H56O8
DaMMarenediol II 3-O-caffeate DaMMarenediol II 3-O-caffeate 171438-55-4 C39H58O5
ent-3β-Hydroxykaur-16-en-19-oic acid ent-3β-Hydroxykaur-16-en-19-oic acid 66556-91-0 C20H30O3
Pterisolic acid E Pterisolic acid E 1401419-89-3 C20H30O5
3,5,7,15-Tetraacetoxy-9-
nicotinoyloxy-6(17),11-jatrophadien-14-one 3,5,7,15-Tetraacetoxy-9- nicotinoyloxy-6(17),11-jatrophadien-14-one 244277-75-6 C34H43NO11
GeloMulide N GeloMulide N 1005212-02-1 C24H32O7
Glutinol acetate Glutinol acetate 6426-44-4 C32H52O2
2-Acetoxy-3-deacetoxycaesaldekarin E 2-Acetoxy-3-deacetoxycaesaldekarin E 18326-06-2 C24H30O6
6-O-Nicotinoylscutebarbatine G 6-O-Nicotinoylscutebarbatine G 1206805-30-2 C32H36N2O8
9-Deacetyl-9-benzoyl-
10-debenzoyl-4β,20-epoxytaxchinin A 9-Deacetyl-9-benzoyl- 10-debenzoyl-4β,20-epoxytaxchinin A 227011-48-5 C31H40O11
ent-7α,9-Dihydroxy-
15-oxokaur-16-en-19,6β-olide ent-7α,9-Dihydroxy- 15-oxokaur-16-en-19,6β-olide 59885-89-1 C20H26O5
Neocaesalpin L Neocaesalpin L 952473-86-8 C26H36O11
Norcaesalpinin E Norcaesalpinin E 854038-96-3 C21H28O6
(1R,4aS,10aR)-7-Acetyl-1,2,3,4,4a,9,10,10a-octahydro-1,4a-dimethyl-9-oxo-1-phenanthrenecarboxylic acid (1R,4aS,10aR)-7-Acetyl-1,2,3,4,4a,9,10,10a-octahydro-1,4a-dimethyl-9-oxo-1-phenanthrenecarboxylic acid 120591-53-9 C19H22O4
bryonolic acid bryonolic acid 24480-45-3 C30H48O3
8-debenzoylpaeoniflorin 8-debenzoylpaeoniflorin 23532-11-8 C16H24O10
palbinone palbinone 139954-00-0 C22H30O4
1-hydroxy-7,9-dideacetylbaccatin I 1-hydroxy-7,9-dideacetylbaccatin I 142203-64-3 C28H40O12
INGENOL-20-HEXADECANOATE INGENOL-20-HEXADECANOATE 39071-33-5 C36H58O6
Diosbulbin C Diosbulbin C 20086-07-1 C19H22O7
16-Deoxysaikogenin F 16-Deoxysaikogenin F 57475-62-4 C30H48O3
3α-Acetoxy-20-oxo
-29-norlupane-23,28-dioic acid 3α-Acetoxy-20-oxo -29-norlupane-23,28-dioic acid 262272-76-4 C31H46O7
Lup-20(29)-ene-3β,23-diol Lup-20(29)-ene-3β,23-diol 163060-07-9 C30H50O2
XYLOTAXOL B, 7-(P) XYLOTAXOL B, 7-(P) 90352-19-5 C50H61NO18
Pterisolic acid C Pterisolic acid C 1401419-87-1 C20H26O4
GeloMulide B GeloMulide B 122537-60-4 C22H28O6
Yucalexin P-17 Yucalexin P-17 119642-82-9 C20H30O3
Aphadilactone C Aphadilactone C 1522004-70-1 C40H52O8
Jatrophane 1 Jatrophane 1 210108-85-3 C36H45NO13
Mudanpioside J Mudanpioside J 262350-52-7 C31H34O14
21-EPISERRATENEDIOL 21-EPISERRATENEDIOL 1449-06-5 C30H50O2
21-Episerratriol 21-Episerratriol 24513-57-3 C30H50O3
9-Deacetyl-9-benzoyl-10-debenzoyltaxchinin A 9-Deacetyl-9-benzoyl-10-debenzoyltaxchinin A 172486-22-5 C31H40O10
Epitulipinolide diepoxide Epitulipinolide diepoxide 39815-40-2 C17H22O6
15-Oxo-9-hydroxykaur-16-en-18-oic acid 15-Oxo-9-hydroxykaur-16-en-18-oic acid 77658-39-0 C20H28O4
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