Showing posts with label organic chemistry. Show all posts
Showing posts with label organic chemistry. Show all posts

Saturday 2 August 2014

Your Aunt can teach you Organic Opectroscopy

Organic spectroscopy should be brushed up and you get confidence

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Organic chemists from Industry and academics to interact on Spectroscopy techniques for Organic compounds ie NMR, MASS, IR, UV Etc. email me ……….. amcrasto@gmail.com
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Oleanolic acid spectral data and interpretation

 http://orgspectroscopyint.blogspot.in/2014/08/oleanolic-acid-spectral-data-and.html
Chemical structure for Oleanolic AcidOleanolic acidOleanolic acid
(4aS,6aR,6aS,6bR,8aR,10S,12aR,14bS)-10-hydroxy-2,2,6a,6b,9,9,12a-heptamethyl-1,3,4,5,6,6a,7,8,8a,10,11,12,13,14b-tetradecahydropicene-4a-carboxylic acid
Oleanic acid, Caryophyllin, Astrantiagenin C, Giganteumgenin C, Virgaureagenin B, 3beta-Hydroxyolean-12-en-28-oic acid, OLEANOLIC_ACID
Molecular Formula: C30H48O3
Molecular Weight: 456.70032
Ursolic acid [(3b)-3-Hydroxyurs-12-en-28-oic acid] rarely occurs without its isomer oleanolic acid [(3b)-3-Hydroxyolean-12-en-28-oic acid] They may occur in their free acid form, as shown in Figure 1, or as aglycones for triterpenoid saponins which are comprised of a triterpenoid aglycone linked to one or more sugar moieties. Ursolic and oleanolic acids are similar in pharmacological activity
A pentacyclic triterpene that occurs widely in many PLANTS as the free acid or the aglycone for many SAPONINS. It is biosynthesized from lupane. It can rearrange to the isomer, ursolic acid, or be oxidized to taraxasterol and amyrin.
MS
EIMS m/z (rel. int.) 456 [M]+ (5), 412 (3), 248 (100), 203 (50), 167 (25), 44 (51)
IR KBR
(KBr) 3500, 2950, 2850, 1715; 1H-NMR (250 MHz, pyridine-d5)
δ: 5.49 (1H, s, H-12),
3.47 (1H, t, J = 8.0 Hz, H-3), 3.30 (1H, m, H-18), 1.12 (3H, s, CH3-27),
0.96 (3H, s, CH3-30), 0.91 (3H, s, CH3-25), 0.89 (3H, s, CH3-23),
0.87 (3H, s, CH3-24), 0.75 (3H, s, CH3-26)
1H NMR
(250 MHz, pyridine-d5)δ: 5.49 (1H, s, H-12), 3.47 (1H, t, J = 8.0 Hz, H-3),
3.30 (1H, m, H-18), 1.12 (3H, s, CH3-27), 0.96 (3H, s, CH3-30),
0.91 (3H, s, CH3-25), 0.89 (3H, s, CH3-23), 0.87 (3H, s, CH3-24), 0.75 (3H, s, CH3-26)
13 C NMR
(63 MHz, pyridine-d5) δ: 180.2 (C-28), 144.8 (C-13), 122.5 (C-12), 78.0 (C-3), 55.7 (C-5), 48.0 (C-9), 46.6 (C-8, 17), 42.1 (C-14), 39.7 (C-4), 39.4 (C-1), 37.3 (C-10), 33.2 (C-7), 32.9 (C-29), 32.4 (C-21), 30.9 (C-20), 28.7 (C-23), 27.2 (C-2), 26.9 (C-15), 26.1 (C-30), 23.7 (C-11), 23.6 (C-16), 18.7 (C-6), 17.4 (C-26), 16.5 (C-24), 15.5 (C-25)
FIG. 4 shows the 1H NMR spectrum of oleanolic acid;
FIG. 5 shows the 13C NMR spectrum of oleanolic acid;
FIG. 6 shows the 13C DEPT NMR spectrum of oleanolic acid;
FIG. 7 shows the 113C HSQC NMR spectrum of oleanolic acid;
see below
EXAMPLE 2 Extraction and Isolation of Oleanolic Acid (9) and Maslinic Acid (10) from Cloves
Syzygium aromaticum dried buds or whole cloves were obtained commercially. The cloves (1.5 kg, whole) of Syzygium aromaticum were sequentially and exhaustively extracted with hexane and ethyl acetate to give, after solvent removal in vacuo, a hexane extract (68.8 g, 4.9%) and an ethyl acetate extract (34.1 g, 2.3%). A portion of the ethyl acetate extract (10.0 g), was subjected to chromatographic separation on silica gel (60-120 mesh) column (40×5.0 cm). Elution with hexane/ethyl acetate solvent mixtures (8:2→6:4) afforded pure oleanolic acid (9) (4.7 g, 1.06%), a mixture of oleanolic acid (9) and maslinic acid (10) (0.5 g), and pure maslinic acid (10) (0.25 g). The structures of oleanolic acid (9) and maslinic acid (10) (as 2,3-diacetoxyoleanolic acid) were confirmed by spectroscopic data analysis (1D and 2D 1H NMR and 13C NMR experiments) (FIGS. 4-7 and FIGS. 8-10, respectively).
ANTHONY MELVIN CRASTO
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Friday 10 January 2014

Recent advances on diversity oriented heterocycle synthesis via multicomponent tandem reactions based on A3 coupling



Recent advances on diversity oriented heterocycle synthesis via multicomponent tandem reactions based on A3 coupling (14-8183LR) [pp. 1-20]
Arkivoc 2014 Part (i), 1-20: Special Issue 'Reviews and Accounts'
Yunyun Liu
Full Text: PDF (235K)
http://www.arkat-usa.org/get-file/48824/
Recent advances on diversity oriented heterocycle synthesis via
multicomponent tandem reactions based on A3 coupling

Yunyun Liu*
a,b

a Key Laboratory of Functional Small Organic Molecule, Ministry of Education,
Jiangxi Normal University, Nanchang 330022, P. R. China
b College of Chemistry and Chemical Engineering, Jiangxi Normal University,
Nanchang 330022, P. R. China

Abstract
A3 coupling reactions are the reactions between aldehydes, amines and alkynes, which yield
propargylamine derivatives under various catalyst conditions. By making use of the versatile
reactivity of propargylamines, tandem reactions initiated by the functional group(s) in the in situ
generated propargylamines constitute one of the most important applications of A3
 couplings.
These tandem reactions are especially useful for the synthesis of heterocyclic compounds. In this
review, the progress on multicomponent tandem reactions based on A3
 coupling is summarized.



Author’s Biography


Dr. Yunyun Liu was born in 1983 in Shandong Province, China. She obtained her Bachelor
Degree in Qufu Normal University in 2005. She then moved to Zhejiang University to continue
her graduate study in the Department of Chemistry. Under the supervision of Professor Weiliang
Bao, she worked on the field of copper-catalyzed Ullmann coupling reaction and related tandem
reactions for her doctorate study. She obtained her doctorate degree in 2010 and presently she is
an assistant professor in Jiangxi Normal University. She is currently interested in the research of
metal-catalyzed organic synthesis and the development of new cascade organic reactions.

Friday 29 November 2013

Saturday 16 November 2013

Here’s an improved synthesis of benzazepines



Benzazepines are heterocyclic chemical compounds consisting of a benzene ring fused to an azepinering. Examples include benazeprilfenoldopamlorcaserin and varenicline

Benzazepines at the US National Library of Medicine Medical Subject Headings (MeSH)

Benzazepines such as compound 3are intermediates for synthesizing drugs used to treat heart and kidney disorders. Y. Torisawa and co-inventors state that existing methods for preparing the intermediates are inefficient for industrial production because of low yields and purity.
The route they used for preparing 3 is the reaction of chlorotetrahydrobenzazepine 1with bromoaniline derivative 2 in the presence of CO and a Pd–Ph3P catalyst (Figure 1); DBU is 1,8-diazabicyclo[5.4.0]undec-7-ene. The product is isolated, purified by column chromatography, and recovered in 85% yield and 99.1% purity. The patent contains 1H and 13C NMR, IR, and mass spectroscopy data.

The reaction gives small quantities (≈0.01–0.03 wt%) of four byproducts that are formed by the reaction of 3 with 1. These compounds are easily separated from 3, and their 1H NMR data are reported.
The inventors also describe the synthesis of 2 and several structurally related compounds by routes outlined in Figure 2. The preparation of 2 begins with the condensation of toluidine 4 and benzoyl chloride 5 in the presence of NaOH to form amide 6, isolated in 96.6% yield. In the second step, 6 is brominated in HOAc, and 2 is isolated in 97% yield. Although the purities of 2 and 6 are not reported, both have sharp melting points; 1H NMR data are provided.


Compound 6 can also be used to prepare acid 7 by treating it with (COCl)2 in the presence of AlCl3, and then hydrolyzing the product. The crude acid is isolated, treated with aq NaOH, and recovered in 65.8% yield and 99.4% purity after recrystallization from MeOH.
The reaction of 6 and AcCl in the presence of AlCl3 gives compound 8, isolated in 66.8% yield. The purity is not reported, but the compound has a sharp melting point, and 1H NMR data are given. Oxidizing 8 with NaOCl forms 7, which is isolated in 77.2% yield and 99.8% purity after recrystallization from MeOH.

A key feature of the processes described in this patent is the commercial availability of starting materials 1 and 2. The inventors claim that the processes give the desired compounds in higher yields and purities than existing methods. (Otsuka Pharmaceutical [Tokyo]. US Patent 8,273,735, )

Process for preparing benzazepine compounds or salts thereof

www.google.co.in/patents/US8273735
Grant - ‎Filed 1 Sep 2006 - ‎Issued 25 Sep 2012 - ‎Yasuhiro Torisawa - ‎Otsuka Pharmaceutical Co., Ltd.
This invention provides a process for preparing benzazepine compounds of the formula (1): wherein X1 is a halogen atom, R1 and ...


Paper | Regular issue | Vol 53, No. 9, 2000, pp.2009-2018
Published online: 
DOI: 10.3987/COM-00-8982
■ A Synthesis of 2,3,4,5-Tetrahydro-1H-3-benzazepines via Pummerer-Type Cyclization of N-(2-Arylethyl)-N-(2-phenylsulfinylethyl)formamides
Jun Toda, Tsuyoshi Ichikawa, Toshiaki Saitoh, Yoshie Horiguchi, and Takehiro Sano*
*Showa Pharmaceutical University, 3-3165, Higashi-tamagawagakuen, Machida, Tokyo 194-8543, Japan
Abstract
A construction of 2,3,4,5-tetrahydro-1H-3-benzazepine ring system (7) was achieved via Pummerer-type cyclization of N-(2-arylethyl)-N-2- (phenylsulfinylethyl)formamides (6). This route produced the benzazepines (10) and (11) in six steps starting from readily available 2-arylethylamines (2) and 2-chloroethyl phenyl sulfide. 
PDF (61KB)