.alpha.-Bergamotenes in oil of black pepper

Russell, G.; Murray, Wallace J.; Müller, Carlos J.; Jennings, Walter

doi:10.1021/jf60160a031

Cited by 41 publications

(12 citation statements)

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(1 reference statement)

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“…The crude acetate was purified by column chromatography on silica gel (5 g) with pentane-ether (7:3 V/V) to give 85 mg (91%) of pure acetate 9, which was identical by IR, NMR, and VPC with an authentic sample prepared p r e v i o~s l y :~~ IR (cc14) 3025,1740, 1470, 1445,1440, 1385, 1375, 1360,1250, 1240,1230, added and the mixture was extracted with pentane. The organic extracts were washed with brine, dried (Na2S04), filtered through silica gel (2 g), and then concentrated to give 31 mg (73%) of 1 which was purified by preparative VPC on 5% SE-30; the IR spectrum of this synthetic material was identical with that published2c for the natural material; N M R (CDC13) 60.84 (s, 3), 1.20 (d, 1, J = 8 Hz), 1.5-1.8 (m, 9), 1. 7-2.5 (m, 9), and 5.4-5.0 ppm (m, 2); mass spectrum m/e (re1 intensity) 204 (molecular ion, 24), 119 (IOO), 93 (78).…”

Section: Endo-6-carbamoyl-26-dimethyibicyclo[3ll]hept-2-ene (29a)mentioning

confidence: 99%

“…This scheme may be divided into four LL 12 10 -stages: (1) preparation of suitably substituted bicyclo [3.2.1]-octanones 10; (2) formation of the required cyclobutane ring via intramolecular ring closure9 of IO (see arrows) to give tricyclo [3.2.1 .03,6]octan~ne~ l l ; (3) fragmentation of the 1,3-dioxygen moiety of 11 as shown to generate directly the desired 2-methylbicyclo[3.1. Ilhept-2-ene skeletons 12 with stereocontrolled, differentiated functionality at the quaternary C-6 center; and (4) appropriate functional group modification.…”

Section: Samuel D Larsedb and Stephen A Monti*mentioning

confidence: 99%

“…The organic phase was dried (MgS04) and filtered through neutral aluminum oxide (50 g, activity 111) using methylene chloride (700 mL). After concentration at reduced pressure, the solid residue was crystallized from benzene to give 6.0 g (73%) of 16c: mp 130-1 32 OC;IR(KBr) 1730cm-I;NMR(CDCI3)6 1.12(d,3,J= 7Hz), 1.62 (s, 3), 1.6-2.6, 2.10 (m, s, 9), 3.07 (s, 3) …”

Section: 7-dimethyl-exo-4-hydroxy-exo-3-methanesulfonatobicyclo-[3mentioning

confidence: 99%

“…A solution of LiAIH4 (50 mg,13 mmol) in ether (8 mL) was added to a stirred solution of tricyclic ketone 2lb (208 mg, 8.7 mmol) in ether ( I O mL) at 0 "C. After 20 min ethyl acetate (1 .O g) was added followed by a cold saturated sodium potassium tartrate solution (50 mL). The mixture was extracted with ether and the combined extracts were washed with brine, dried (MgSOd), and evaporated under reduced pressure to give 205 mg (97%) of the crude alcohol 27a: IR (CC14) 3600 cm-I; NMR (CDCI3) 6 0.14 (s, 9), 1.28 (s, 3), 1.57 (s, 3), 1. 5-2.3 (m, 7), 2.38 (s, l), and 3.76 ppm (m, 1).…”

Section: B a Solution Of 2lb (326 Mg 136 Mmol) In T H F (3 Ml) Wasmentioning

confidence: 99%

“…15-1.3 (m, l) Aldehyde 32s (I48 mg, 0.98 mmol) in benzene (5 mL) was added to Dibal in benzene (25%, 2 mL, 3 mmol) and the mixture was stirred for 15 min at room temperature. After workup as described above, the crude product was purified by chromatography on silica gel (1 0 g) using pentane-ether (1 : 1 v/v) to give 1 10 mg (74%) of liquid alcohol 33a: IR (CH2C12) 3630, 3020, 1435, 1025 cm-l; NMR (CDCI3) 1.27, 1.24 (s, d, 2 , J = 8 Hz), 1.35 (s, 3), 1.72 (m, 3), 1. 9-2.7 (m, 5 ) , an AB quartet with doublets centered at 3.59 and 3.37, 5.27 Anal.…”

Section: Endo-6-carbamoyl-26-dimethyibicyclo[3ll]hept-2-ene (29a)mentioning

confidence: 99%

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Total synthesis of racemic .alpha.-trans- and .alpha.-cis-bergamotene and .alpha.-pinene

Larsen¹,

Monti²

1977

J. Am. Chem. Soc.

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The stereoselective total synthesis of racemic a-trans-(1) and of racemic a-cis-(2) bergamotene and the direct preparation of racemic a-pinene (3) from 4-methylbicyclo[3.2. IIoct-3-en-6-one (14) are described. The key steps involve formation of the cyclobutane ring by intramolecular ring closure of the bicyclic precursors 16d and 18 and sodium amide initiated fragmentation of the 8-trimethylsilyloxy ketone moiety of the resulting tricyclic derivatives 21b and 22 to give the required 2-methylbicyclo[3.1. I ] hept-2-ene skeletons 29 which contain stereocontrolled, differentiated functionality at the quaternary C-6 center. Functional group modification of 29 then completes the fully stereocontrolled, total synthesis of these natural substances.The mono-and sesquiterpenes comprising the pinane family of natural products are characterized structurally by the presence of a bicyclo[3.1. ]]heptane nucleus. The widely distributed essential oil hydrocarbon a-trans-bergamotene2 (1) and its cis isomer3 (2) are representative of the known sesquiterpenes: while the ubiquitous a-pinene (3) and the highly oxygenated paeoniflorin5 (4) are illustrative of the structural c6H5c02B Gluo I ~~= a i~~(~~( -c ( a i~)~, at^ 4 2 R1=M3, R z = O~& H~~I -C C M~)~ 3 R1=R2=043variety found in the monoterpene members of this family. Previous synthetic efforts have resulted in the preparation of the three a hydrocarbons 2,' and 3,8a*c although the fundamental synthetic objectives presented by these substances, (1) the direct construction of the acid-labile 2-methylbicyclo[3.1 .l]hept-2-ene skeleton and (2) the unambiguous stereocontrol of the quaternary C-6 carbon center, have only been partially achieved by these earlier endeavors.Three basic routes have been used to prepare the symmetrically substituted 6,6-dimethylbicyclo[ 3.1. I] heptane nucleus: formation of the three-carbon bridge by ring closure of a cyclobutane substrate;8a,b preparation of the one-carbon bridge by intramolecular alkylation of a cyclohexanone derivative;8c and intramolecular photochemical [2 + 21 cycloaddition of an acyclic precursor.8d Of these, a photochemical [2 + 21 cycloaddition was employed as the key step in the synthesis of a-trans-bergamotene (1) to prepare a mixture of C-5 isomers 5 (5:3) in which the desired trans isomer predominated (eq trans/cis = 5 : 3 5

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Section: Endo-6-carbamoyl-26-dimethyibicyclo[3ll]hept-2-ene (29a)mentioning

confidence: 99%

Section: Samuel D Larsedb and Stephen A Monti*mentioning

confidence: 99%

Section: 7-dimethyl-exo-4-hydroxy-exo-3-methanesulfonatobicyclo-[3mentioning

confidence: 99%

Section: B a Solution Of 2lb (326 Mg 136 Mmol) In T H F (3 Ml) Wasmentioning

confidence: 99%

Section: Endo-6-carbamoyl-26-dimethyibicyclo[3ll]hept-2-ene (29a)mentioning

confidence: 99%

See 3 more Smart Citations

Total synthesis of racemic .alpha.-trans- and .alpha.-cis-bergamotene and .alpha.-pinene

Larsen¹,

Monti²

1977

J. Am. Chem. Soc.

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Co‐Adsorption of Copper(II) and 3‐Amino‐1,2,4‐triazole at a Water–Natural Macromolecular Compound Interface: Molecular Structure from Adsorption Isotherms Combined with X‐ray Absorption Measurements

Flogeac

Aplincourt

2005

Eur J Inorg Chem

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The co-adsorption of Cu II and amitrole at a water-natural macromolecular compound interface was studied by means of batch adsorption experiments, Fourier transform infrared, and X-ray absorption spectroscopy. The binary systems, aqueous amitrole-Cu II complex, and amitrole and Cu II adsorbed on the surface of the solid were studied. The ternary system was investigated over the pH range 2-10 and at varying metal concentrations. The combination of macroscopic and molecular information shows that Cu II and amitrole interact directly at the water-solid interface to form ternary surface complexes. A two-step mechanism is proposed whereby initial formation of a Cu II -amitrole aqueous com-

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Sesquiterpenoids from Costus Root Oil (Saussurea lappa CLARKE)

Maurer

Grieder

1977

Helvetica Chimica Acta

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Apart from the well‐known constituents (+)‐β‐selinene (2), (−)‐β‐elemene (4), (+)‐β‐costol (7), (−)‐caryophyllene (17), and (−)‐elemol (19) the following sesquiterpenoids have been isolated for the first time from costus root oil (Saussurea lappa CLARKE): (−)‐α‐selinene (1), (+)‐selina‐4, 11‐diene (3), (−)‐α‐trans‐bergamotene (5), (−)‐α‐costol (6), (+)‐γ‐costol (8), (−)‐elema‐1,3,11 (13)‐trien‐12‐ol (9), (−)‐α‐costal (11), (+)‐γ‐costal (12), (+)‐γ‐costal (13), (−)‐elema‐1,3,11 (13)‐trien‐12‐al (elemenal, 14), (−)‐(E)‐trans‐bergamota‐2, 12‐dien‐14‐al (15), (−)‐ar‐curcumene (16), and (−)‐caryophyllene oxide (18). Compounds 6, 8, 9, and 13 are new sesquiterpenoids. IR. and NMR. spectra of 12 sesquiterpenoids are reproduced.

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.alpha.-Bergamotenes in oil of black pepper

Cited by 41 publications

References 1 publication

Total synthesis of racemic .alpha.-trans- and .alpha.-cis-bergamotene and .alpha.-pinene

Total synthesis of racemic .alpha.-trans- and .alpha.-cis-bergamotene and .alpha.-pinene

Co‐Adsorption of Copper(II) and 3‐Amino‐1,2,4‐triazole at a Water–Natural Macromolecular Compound Interface: Molecular Structure from Adsorption Isotherms Combined with X‐ray Absorption Measurements

Sesquiterpenoids from Costus Root Oil (Saussurea lappa CLARKE)

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