Structure determination of cyclopentane terpene derivatives by crossed NMR and MS techniques

Pianet, Isabelle; Dolatkhani, Marc; Cramail, Henri; Deffieux, Alain; Bourgeois, Guy

doi:10.1051/jcp/1995921813

Cited by 2 publications

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“…[5,13,14,18,22] The chromatogram of the mixture of pyrolysis products obtained from 2 in Figure 1 shows that product 4 was formed exclusively from 2, whereas 5 resulted from the thermal rearrangement of 3. In addition, monocyclic products (trans-D8-p-menthene, 6; cis-D8-p-menthene, 7, and carvomenthene, 8; Scheme 1) were found in the mixture of pyrolysis products of both pinane isomers.…”

Section: Resultsmentioning

confidence: 99%

“…As found for 4 b and 4 d and indicated in Table 1, when both groups are placed on the same side of the ring (cis configuration) the proton spectrum shows two singlets, each singlet representing one proton. [22][23][24][25][26] Otherwise (trans configuration) the 1 H NMR spectrum shows only one signal representing both =C Obviously, 4 a and 4 d differ extremely with regard to their stereochemistry, leading to the conclusion that 4 a has to have a trans,trans-configuration, whereas 4 d has to be cis,cis-configured (Table 1). [13,22] Determination in the case of 4 b an 4 c was possible upon consideration that only a total of four combinations of cis or trans are possible.…”

Section: Resultsmentioning

confidence: 99%

“…Absolute configurations were assigned by comparing the enantiomeric excess (ee) of the products of 4 with the ee of 2 used herein, assuming that their formations are enantiospecific. [13,22,26] Isomerization of 3 leads to the formation of three different products: 5 a, 5 b, and 5 c with residence times of 6.4, 7.4, and 8.0 min, respectively (Figure 1), which were separated by using preparative GC. Because of their low concentrations it was not possible to identify the structures for 5 a and 5 c, whereas the configuration of 5 b was elucidated based on (Table 1) the proton NMR spectrum showed two singlets for the =CH 2 group in 5, which enabled the conclusion that the isopropenyl group is located cis to either the methyl group at C 1 or C 2 .…”

Section: Resultsmentioning

confidence: 99%

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Thermal Isomerization of (+)‐cis‐ and (−)‐trans‐Pinane Leading to (−)‐β‐Citronellene and (+)‐Isocitronellene

Stolle

Ondruschka

Bonrath

et al. 2008

Chemistry A European J

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Catalyzed and uncatalyzed rearrangement reactions of terpenoids play a major role in laboratory and industrial-scale synthesis of fine chemicals. Herein, we present our results on the thermally induced isomerization of pinane (1). Investigation of the thermal behavior of (+)-cis- (1 a) and (-)-trans-pinane (1 b) in a flow-type reactor reveals significant differences in both reactivity and selectivity concerning the formation of (-)-beta-citronellene (2) and (+)-isocitronellene (3) as main products. Possible explanations for these results are discussed on the basis of reaction mechanism and ground-state geometries for 1 a and 1 b. To identify side reactions caused from ene cyclizations of 2 and 3, additional pyrolysis experiments were conducted that enabled the identification of almost all compounds in the network of C(10)H(18)-hydrocarbon products formed from 1.

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Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

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Thermal Isomerization of (+)‐cis‐ and (−)‐trans‐Pinane Leading to (−)‐β‐Citronellene and (+)‐Isocitronellene

Stolle

Ondruschka

Bonrath

et al. 2008

Chemistry A European J

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“…272 Pyrolysis of 3(10)-dihydromyrcene 49 afforded all four diastereoisomers of the cyclopentane 50, and three of these have been purified and characterised by their NMR and mass spectra. 273 The imino allene 51 cyclises to yield the cyclopentene 52 when it is heated at 250 C, and this then undergoes further cyclisation to give the bicyclic amine 53. 274 A practical route for the conversion of (S)-citronellol ent-37 into (3S)-methylheptanoic acid 54 has been described.…”

Section: 6-dimethyloctanesmentioning

confidence: 99%

Monoterpenoids

Grayson¹

1998

Nat. Prod. Rep.

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Species Principal constituents ReferenceAbies balsamea Mill -and -pinene, -phellandrene, limonene Achillea biebersteinii Afan piperitone, or cineol and camphor Aloysia triphylla (L'Herit.) Britton citral, limonene Alpinia conchigera Griff. cineol Alseuosmia macrophylla A. Cunn. flowers: linalool Ambrosia microcephala DC. camphor, bornyl acetate Amomum subulatum Roxb. cineol, -terpineol, -and -pinene Artemisia afra yomogi alcohol, artemisyl acetate Artemisia afra Willd. cineol, terpinen-4-ol, borneol Artemisia ordosica -and -pinene, sabinene Austromyrtus dulcis (C. T. White) L. S. Smith (chemotype) -pinene, cineol Boronia megastigma Nees. -ionone, 8-hydroxylinalyl esters, geranyloxy cinnamate Bouea macrophylla Griff. ( E)--ocimene, -pinene Calamintha cretica piperitenone, piperitenone oxide Calamintha incana (Sm.) Boiss. piperitenone oxide Callistemon speciosus Anthor. cineol, -pinene, -terpineol Canella winteriana Gaertn. stem and bark: cineol, terpinen-4-ol, -terpinyl acetate, -terpineol; leaves: myrcene Cedronella canariensis Webb et Berth. ssp. canariensis pinocarvone Chamelaucium uncinatum genotypes -pinene, citronellal, limonene, linalool, -terpinyl acetate Chenopodium ambrosioides limonene, trans-pinocarveol Chenopodium botrys -8 Chrysanthemum balsamata carvone, camphor Chrysanthemum lavandulaefolium menthol Cinnamomum camphora Nees et Ebermaier camphor, cineol, terpinen-4-ol, limonene Cinnamomum puciflorum -2 Citrus grandis limonene Clausena anisata (Willd.) J. D. Hook limonene, myrcene Coleus aromaticus carvacrol, camphor Coreopsis barteri Oliv. & Hiern limonene, -phellandrene Coreopsis grandis Hogg ex Sweet myrcene Coriandrum sativum seeds: linalool Coridothymus capitatus Reich. f. carvacrol 98, 99 Cunila fasiculata menthofuran Cunila microcephala menthofuran, limonene Curcuma aeruginosa Roxb. cineol, camphor Curcuma amada Roxb. myrcene Curcuma aromatica Salisb. cineol, camphor, isoborneol, camphene Curcuma cochinchinensis Gagnep. cineol Curcuma domestica -phellandrene, cineol, p-cymene, -pinene Curcuma pierreana Gagnep. Rhizome, stem: isoborneol, isobornyl acetate leaf: isoborneol, camphor Croton aubrevillei J. Leonard linalool Croton zambesicus Muell. Arg. linalool Cyclotrichum origanifolium (Labill.) Manden. et Scheng. cis-isopulegone, pulegone, isomenthone, menthol Cymbopogon caesius (Nees et Hook. et Arn.) Stapf. perillyl alcohol, geraniol, limonene Cymbopogon citratus (DC.) Stapf. citral, geraniol, myrcene, -and -pinene Cymbopogon khasianus (Munro ex Hack.) Bor. geraniol, geranyl acetate, linalool Cymbopogon schoenanthus piperitone, limonene Daphne mezereum flowers: linalool, linalyl oxides Echinophora chryantha Freyn et Sint. -phellandrene Egletes viscosa various terpenol acetates Elsholtzia ciliata (Thunb.) Hyland chemotype (a): elsholtzia ketone, -thujone chemotype (b): neral, geranial, limonene

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Structure determination of cyclopentane terpene derivatives by crossed NMR and MS techniques

Cited by 2 publications

References 0 publications

Thermal Isomerization of (+)‐cis‐ and (−)‐trans‐Pinane Leading to (−)‐β‐Citronellene and (+)‐Isocitronellene

Thermal Isomerization of (+)‐cis‐ and (−)‐trans‐Pinane Leading to (−)‐β‐Citronellene and (+)‐Isocitronellene

Monoterpenoids

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