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Showing posts with label COSY. Show all posts
Showing posts with label COSY. Show all posts

Tuesday, 5 December 2017

Continuous-Flow Preparation of γ-Butyrolactone Scaffolds, 2-(5,5-dimethyl-2-oxotetrahydrofuran-3- yl)acetic acid

(5,5-dimethyl-2-oxotetrahydrofuran-3-yl)acetic acid
2-(5,5-Dimethyl-2-oxotetrahydrofuran-3-yl)acetic acid
2-carboxymethyl-4-methyl-4-pentanolide,
str3



2-(5,5-Dimethyl-2-oxotetrahydrofuran-3-yl)acetic acid (4a).
1H NMR (DMSO-d6, 400 MHz): δ = 3.20 – 3.10 (m, 1H), 2.62 (dd, J = 17.1, 4.4 Hz, 1H), 2.54 – 2.45 (m, 1H), 2.31 – 2.21 (m, 1H), 1.84 (t, J = 12.0 Hz, 1H), 1.39 (s, 3H), 1.33 (s, 3H) ppm.
13C NMR (DMSO-d6, 100.6 MHz): δ = 177.2, 172.5, 82.2, 39.8, 36.7, 34.0, 28.4, 26.6 ppm.
The 1H NMR data did not match those reported in the literature. S7 IR (neat): νmax = 2980, 2935, 1728, 1707 cm- 1 .
MP: 132.1-133.8 °C (lit.S8 137-140 °C).
[S7] Kochikyan, T. V.; Arutyunyan, E. V.; Arutyunyan, V. S.; Avetisyan, A. A. Russ. J. Org. Chem. 2002, 38, 390–393.
[S8] Phillips, D. D.; Johnson, W. A. J. Am. Chem. Soc. 1955, 77, 5977–5982.
ESI HRMS m/z C8H11O4 - [M-H]- : calcd 171.0652. Found 171.0653.

Continuous-Flow Preparation of γ-Butyrolactone Scaffolds from Renewable Fumaric and Itaconic Acids under Photosensitized Conditions

 Center for Integrated Technology and Organic Synthesis, Department of Chemistry, University of Liège, B-4000 Liège (Sart Tilman), Belgium
 Corning Reactor Technologies, Corning SAS, 7 bis Avenue de Valvins, CS 70156 Samois sur Seine, 77215 Avon Cedex, France
§ XStruct, Department of Chemistry, Ghent University, Krijgslaan 281-S3, B-9000 Ghent, Belgium
Org. Process Res. Dev., Article ASAP
DOI: 10.1021/acs.oprd.7b00314
 

Abstract

Abstract Image
The method and results described herein concern the photosensitized addition of various alcohols to renewable platform fumaric and itaconic acids under scalable continuous-flow conditions in glass micro- and mesofluidic reactors. Alcohols were used both as reagents and as solvents, thus contributing to a reduced environmental footprint. Process parameters such as the temperature, light intensity, and the nature as well as amount of the photosensitizer were assessed under microfluidic conditions and, next, transposed to a lab-scale mesofluidic reactor connected with an in-line NMR spectrometer for real-time reaction monitoring. Substituted γ-butyrolactones, including spiro derivatives with unique structural features, were obtained with quantitative conversion of the starting materials and in 47–76% isolated yields. The model photoaddition of isopropanol to fumaric acid was next successfully transposed in a pilot-scale continuous-flow photoreactor to further demonstrate scalability.
JC M. Monbaliu, PhD.
Department of Chemistryjc.monbaliu@ulg.ac.be
t +32 (0) 4 366 35 10Image result for Jean-Christophe M. Monbaliu
 Center for Integrated Technology and Organic Synthesis, Department of Chemistry, University of Liège, B-4000 Liège (Sart Tilman), Belgium
Romaric Gérardy

Romaric Gérardy

PhD Student at Université de Liège
Center for Integrated Technology and Organic Synthesis (CiTOS)
 Université de Liège, Liège Area, Belgium
 
Image result for Kristof Van Hecke
XStruct, Department of Chemistry, Ghent University, Krijgslaan 281-S3, B-9000 Ghent, Belgium
Kristof.VanHecke@UGent.be
Group leader of the XStruct group
Image result for Alessandra Vizza
Corning Reactor Technologies, Corning SAS, 7 bis Avenue de Valvins, CS 70156 Samois sur Seine, 77215 Avon Cedex, France
Image result for Marc Winter corning
Marc Winter
Senior Application Engineer - Advanced-Flow(tm) Reactors
CorningFontainebleau, France
Corning Reactor Technologies, Corning SAS, 7 bis Avenue de Valvins, CS 70156 Samois sur Seine, 77215 Avon Cedex, France
Clemens Horn at Corning SAS
Clemens Horn, Senior Research Scientist
Corning SAS
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Saturday, 28 October 2017

Ethyl-2-butenoate

Abstract

For the last fifty years nuclear magnetic resonance spectroscopy, generally referred as NMR, is one of the most versatile techniques for elucidation of structure of organic compounds. Among all available spectrometric methods, NMR is the only technique which offers a complete analysis and interpretation of the entire spectrum. Due to improved experimental technology and novel approaches, over the last decade nuclear magnetic resonance (NMR) has shown a tremendous progress. Generally, NMR spectroscopy makes use of three approaches; those are one dimension (1D), two dimensions (2D) and three dimensions (3D). Usually, the first approach of 1D-NMR (1H DEPT, 13C, 15N, 19F, 31P, etc.) generates good information about the structure of simple organic compounds, but in case of larger molecules the 1D-NMR spectra are generally overcrowded. Hence, the second approach of 2D-NMR (COSY, DQFCOSY, MQFCOSY, HETCOR, HSQC, HMQC, HMBC, TOCSY, NOESY, EXSY, etc.) is used for the further larger molecules, but 2D-NMR spectra also becomes complex and overlapping when used for further very large molecules like proteins. Hence, so as to achieve high resolution and reduced overlapping in spectra of very large molecules, Multi Dimensional-NMR (Homonuclear and Heteronuclear) are generally used. This paper supports interpretation of structure of different organic compounds by different NMR techniques.



Image result for nmr examples solutions




13C-NMR proton decoupled spectrum of Ethyl-2-butenoate in CDCl3.



DEPT spectrum of Ethyl-2-butenoate.




COSY







https://www.omicsonline.org/structural-elucidation-of-small-organic-molecules-by-1d-2d-and-multi-dimensional-solution-nmr-spectroscopy-2155-9872.S11-001.php?aid=12051&view=mobile
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Structural Elucidation of Small Organic Molecules by 1D, 2D and Multi Dimensional-Solution NMR Spectroscopy

Neeraj Kumar Fuloria* and Shivkanya Fuloria
Anuradha College of Pharmacy, Amravati University, Maharashtra, India
*Corresponding Author:
Dr. Neeraj Kumar Fuloria 
M.Pharm (Pharmaceutical Chemistry)
Head, M.Pharm (Quality Assurance)
Anuradha College of Pharmacy
Chikhli, Buldhana, Maharashtra, India
Tel: 8805680423
E-mail: nfuloria@gmail.com, nfuloria@rediffmail.com
Received date: January 10, 2013; Accepted date: January 30, 2013; Published date: February 07, 2013
Citation: Fuloria NK, Fuloria S (2013) Structural Elucidation of Small Organic Molecules by 1D, 2D and Multi Dimensional-Solution NMR Spectroscopy. J Anal Bioanal Tech S11:001. doi: 10.4172/2155-9872.S11-001
Copyright: © 2013 de Francisco TMG, et al. This is an open-access article distributed under the terms of the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original author and source are credited.

Thursday, 20 July 2017

(7R, 8S, 8′S, 7″S, 8″R)-abiesol A 4″-O-β-d-glucopyranoside, capselloside.

(7R, 8S, 8′S, 7″S, 8″R)-abiesol A 4″-O-β-d-glucopyranoside, and it was named capselloside.
Capselloside (1): Brownish gum; [α]25D −34.0 (c = 0.05, MeOH); UV (MeOH) λmax (log ε) 280 (1.4), 228 (3.3), 214 (3.1) nm; IR (KBr) νmax 3261, 2946, 2816, 1638, 1489, 1261 cm−1; CD (MeOH) λmax (Δ ε) 291 (−), 280 (−) 257 (−) 230 (−) 223 (+); 1H (700 MHz) and 13C (175 MHz) NMR data, see Table 1; HR-FABMS (positive-ion mode) m/z: 723.2626 [M + Na]+ (calcd. for C36H44O14Na, 723.2629).
Compound 1 was obtained as a brownish gum. The molecular formula was established as C36H44O14using HR-FABMS, which showed a positive ion [M + Na]+ at m/z: 723.2626 (calcd. for C36H44O14Na, 723.2629, so the molecular formula was deduced to be C36H44O14.
The 1H-NMR spectrum of 1 revealed the presence of two 1,3,4-trisubstituted aromatic rings (δH 7.16 (d, J = 8.3 Hz, H-5′′), 7.15 (d, J = 8.2 Hz, H-5), 7.05 (d, J = 1.7 Hz, H-2), 7.01 (d, J = 1.7 Hz, H-2′′), 6.95 (dd, J = 8.2, 1.7 Hz, H-6), and 6.90 (dd, J = 8.2, 1.7 Hz, H-6″)), a 1,3,4,5-tetrasubstitued aromatic ring (δH 6.76 (s, H-6′), 6.78 (s, H-2′)), two oxygenated methines (δH 5.58 (d, J = 5.9 Hz, H-7) and 4.85 (m, H-7′′)), two oxygenated methylenes (δH 3.85 (m, H-9b), 3.78 (m, H-9a), and 3.88 (m, H-9′′a), 3.68 (dd, J = 10.9, 6.7 Hz, H-9b′′)), a methylene 2.96 ((dd, J = 13.5, 5.0 Hz, H-7′a), and 2.57 (dd, J = 13.3, 11.0 Hz, H-7′b)), three methines (δH 3.48 (m, H-8), 2.75 (sep, J = 6.5, 5.5 Hz, H-8′), and 2.38 (quin, J = 6.9 Hz, H-8″)), three methoxy groups (δH 3.88 (s, 3-OCH3), 3.87 (s, 5′-OCH3) and 3.84 (s, 3′′-OCH3)), and a glucopyanosyl unit (δH 4.91 (d, J = 7.3 Hz, H-1′′′), 3.69 (m, H-6′′′), 3.51 (m, H-2′′′), 3.41 (overlap, H-4′′′, 5′′′) and 3.39 (m, H-3′′′).
The 13C-NMR spectrum displayed 36 carbon signals, including 18 aromatic carbons δC 151.1 (C-3″), 147.9 (C-4′, 3′), 147.8 (C-3), 147.5 (C-4, 4″), 145.5 (C-5′), 139.7 (C-1″), 135.7 (C-1), 134.9 (C-1′), 119.7 (C-6″), 119.5 (C-6), 118.4 (C-6′), 118.2 (C-5″), 118.1 (C-5), 114.7 (C-2′), 111.5 (C-2″) and 111.3 (C-2), three oxygenated carbons δC 88.6 (C-7), 83.9 (C-7″), and 73.5 (C-9′), three methylene carbons δC 65.1 (C-9), 60.5 (C-9″), 33.9 (C-7′) and three methine carbons δC55.7 (C-8), 54.2 (C-8″), 44.0 (C-8′), and, three methoxy carbons (δC 56.9 and 56.8 (×2)), and glucose carbons δc 103.1 (C-1′′′), 78.5 (C-3′′′), 78.4 (C-5′′′), 75.1 (C-2′′′), 71.6 (C-4′′′), and 62.6 (C-6′′′) (Table 1).
Table 1. 1H (700 MHz) and 13C (175 MHz) NMR data of 1 in methanol-d4 (δ in ppm) a.
 
PositionδC, TypeδH (J in Hz)
1135.7, C 
2111.3, CH7.05, d (1.7)
3147.8, C 
4147.5, C 
5118.1, CH7.15, d (8.2)
6119.5, CH6.95, dd (8.2, 1.7)
788.6, CH5.58, d (5.91)
855.7, CH3.48, m
965.1, CH2 
a 3.78, m
b 3.85, m
1′134.9, C 
2′114.7, CH6.78, s
3′147.9, C 
4′147.9, C 
5′145.5, C 
6′118.4, CH6.76, s
7′33.9, CH2 
a 2.96, dd (13.5, 5.0)
b 2.57, dd (13.3, 11.0)
8′44.0, CH2.75, sep (6.5, 5.5)
9′73.5, CH2 
a 3.78, m
b 4.05, dd (8.3, 6.6)
1″139.7, C 
2″111.5, CH7.01, d (1.7)
3″151.1, C 
4″147.5, C 
5″118.2, CH7.16, d (8.3)
6″119.7, CH6.90, dd (8.2, 1.7)
7″83.9, CH4.85, overlap
8″54.2, CH2.38, quin (6.9)
9″60.5, CH2 
a 3.88, m
b 3.68, dd (10.9, 6.7)
Glc-1′′′103.1, CH4.91, d (7.3)
2′′′75.1, CH3.51, m
3′′′78.5, CH3.39, m
4′′′71.6, CH3.41, m
5′′′78.4, CH3.41, m
6′′′62.6, CH3.69, overlap
OCH3 (3″)56.93.84, s
OCH3 (3)56.83.88, s
OCH3 (5′)56.83.87, s
a The assignments were based on HSQC and HMBC experiments.
The 1H- and 13C-NMR spectra (Table 1) were very similar to those of abiesol A [17], except for the presence of a glucose unit in 1. The positions of three methoxy groups were confirmed as 3-OCH3 (δH3.88)/C-3 (δC 147.8), 5′-OCH3 (δC 3.87)/C-5′ (δC 145.5), and 3″-OCH3 (δH 3.84)/C-3″ (δC 151.1). HMBC correlation (H-1′′′ to C-4″) indicated that a D-glucose moiety was linked to C-4″ (Figure 2a), and identified the β form by the coupling constant (J = 7.3 Hz) [18]. The stereochemistry of 1 was assigned on the basis of examination of the CD spectrum in combination with the NOESY experiment. The absolute configurations of C-7 and C-8 were confirmed as 7R and 8S from the positive Cotton effect at 223 nm and the negative effect at 245 and 291 nm in the CD spectrum [19]. The absolute configurations of C-8′/C-7″/C-8″ were identified as 8′S, 7″S and 8R from the negative Cotton effect at 231 nm and 280 nm, respectively (Figure S8, Supplementary Materials) [19]. HMBC correlations and NOESY cross-peaks (Figure 2) reconfirmed the suggested structure of 1. The enzymatic hydrolysis of 1 afforded d-glucose, which was identified by the sign of the specific rotation [α]25D +48.2 (c = 0.03, H2O) and by co-TLC (CHCl3:MeOH:H2O = 2:1:0.1; Rf = 0.21) [20] and the aglycone 1a, which was identified by 1H-NMR and MS data [17]. Thus, the structure of 1 was determined as (7R, 8S, 8′S, 7″S, 8″R)-abiesol A 4″-O-β-d-glucopyranoside, and it was named capselloside.
Molecules 22 01023 g002
Figure 2. Key 1H-1H COSY, HMBC (a) and NOESY (b) correlations of 1.
 
 
Molecules201722(6), 1023; doi:10.3390/molecules22061023
Article
Phenolic Glycosides from Capsella bursa-pastoris (L.) Medik and Their Anti-Inflammatory Activity
Joon Min Cha 1, Won Se Suh 1, Tae Hyun Lee 1, Lalita Subedi 2,3, Sun Yeou Kim 2,3 and Kang Ro Lee 1,*
1
Natural Products Laboratory, School of Pharmacy, Sungkyunkwan University, Suwon 16419, Korea
2
Gachon Institute of Pharmaceutical Science, Gachon University, 191 Hambakmoero, Yeonsu-gu, Incheon 21936, Korea
3
College of Pharmacy, Gachon University, 191 Hambakmoero, Yeonsu-gu, Incheon 21936, Korea
*
Correspondence: Tel.: +82-31-290-7710; Fax: +82-31-290-7730
Received: 16 May 2017 / Accepted: 18 June 2017 / Published: 20 June 2017

성균관대학교 로고

Image result for Gachon Institute of Pharmaceutical Science, Gachon University,

Abstract:

A new sesquilignan glycoside 1, together with seven known phenolic glycosides 28 were isolated from the aerial parts of Capsella bursa-pastoris. The chemical structure of the new compound 1 was elucidated by extensive nuclear magnetic resonance (NMR) data (1H- and 13C-NMR, 1H-1H correlation spectroscopy (1H-1H COSY), heteronuclear single-quantum correlation (HSQC), heteronuclear multiple bond correlation (HMBC), and nuclear overhauser effect spectroscopy (NOESY)) and HR-FABMS analysis. The anti-inflammatory effects of 18 were evaluated in lipopolysaccharide (LPS)-stimulated murine microglia BV-2 cells. Compounds 4 and 7 exhibited moderate inhibitory effects on nitric oxide production in LPS-activated BV-2 cells, with IC50 values of 17.80 and 27.91 µM, respectively.
Keywords:
Capsella bursa-pastoris; Cruciferae; sesquilignan glycoside; anti-inflammatory
 
str1
 
/////////capselloside, nmr, cosy

Sunday, 30 April 2017

Continuous niobium phosphate catalysed Skraup reaction for quinoline synthesis from solketal

STR1
Continuous niobium phosphate catalysed Skraup reaction for quinoline synthesis from solketal
Green Chem., 2017, Advance Article
DOI: 10.1039/C6GC03140D, Paper
Jing Jin, Sandro Guidi, Zahra Abada, Zacharias Amara, Maurizio Selva, Michael W. George, Martyn Poliakoff
Solketal is derived from the reaction of acetone with glycerol, a by-product of the biodiesel industry. We demonstrate the use of NbOPO4 as a catalyst for the conversion of solketal and anilines to quinolines
STR0
STR1
STR2
str3
str4
Synthesis of 4-(quinolin-6-yl methyl)aniline (6a)
The reaction was carried out accordingly to the general procedure. The purification of 4-(quinoline-6-yl methyl)aniline 6a was carried out with a gradient of polarity from 80:20 to 30:70 (v/v) of CyHex:AcOEt as eluent. 1H NMR (400 MHz, CDCl3) δ ppm: 8.85 (dd, J=4.3,1.7Hz, 1H), 8.07 (dd, J=8.3,1.8Hz, 1H), 8.01 (d, J=9.2Hz, 1H), 7.58–7.54 (m, 2H), 7.36 (dd, J=8.3,4.2Hz, 1H), 7.02 (d, J=8.3Hz, 2H), 6.67–6.63 (m, 2H), 4.06 (s, 2H). 13C NMR (100 MHz, CDCl3) δ ppm: 149.9, 147.3, 144.9, 140.7, 135.9, 131.4, 130.6, 130.1, 129.5, 128.5, 126.6, 121.2, 115.5, 41.2. HRMS-ESI for C16H15N2 [M+H]+ calculated 235.1235, found 235.1245.


Continuous niobium phosphate catalysed Skraup reaction for quinoline synthesis from solketal

Abstract

Solketal is derived from the reaction of acetone with glycerol, a by-product of the biodiesel industry. We report here the continuous reaction of solketal with anilines over a solid acid niobium phosphate (NbP), for the continuous generation of quinolines in the well-established Skraup reaction. This study shows that NbP can catalyse all the stages of this multistep reaction at 250 °C and 10 MPa pressure, with a selectivity for quinoline of up to 60%. We found that the catalyst eventually deactivates, most probably via a combination of coking and reduction processes but nevertheless we show the promise of this approach. We demonstrate here the application of our approach to synthesize both mono- and bis-quinolines from the commodity chemical, 4,4′-methylenedianiline.