(2R,3S,4R,5R)-1-(3-((5-(4-Fluorophenyl)thiophen-2-yl)methyl)-4-methylphenyl)-2,3,4,5,6-pentahydroxyhexan-1-one

CAS 1672658-93-3

C24 H25 F O6 S, 460.52

D-Glucopyranose, 1-C-[3-[[5-(4-fluorophenyl)-2-thienyl]methyl]-4-methylphenyl]-

 

 

CAS 1809403-04-0

C24 H25 F O6 S, 460.52

D-Glucose, 1-C-[3-[[5-(4-fluorophenyl)-2-thienyl]methyl]-4-methylphenyl]-

WO2017/93949

 

 

 

(2R,3S,4R,5R)-1-(3-((5-(4-Fluorophenyl)thiophen-2-yl)methyl)-4-methylphenyl)-2,3,4,5,6-pentahydroxyhexan-1-one    12

From the FT-IR spectra of 12 contain a signal at 1674 cm–1, this signal is strongly indicative of a carbonyl ketone being present in 12

In 13C NMR and HMBC correlations spectra, the chemical shift at 199.75 ppm was observed. Analysis of the NMR data  confirmed that the structure of 12 is a ring-opened keto form

Synthesis of (2R,3S,4R,5R)-1-(3-((5-(4-Fluorophenyl)thiophen-2-yl)methyl)-4-methylphenyl)-2,3,4,5,6-pentahydroxyhexan-1-one 12

title compound 12 (84.23% yield) and having 99.4% purity by HPLC;

 

DSC: 160.84–166.44 °C;

 

Mass: m/z 459 (M+–H);

 

IR (KBr, cm–1): 3313, 2982, 1674.7, 1601, 1507.5, 1232.7;

 

1H NMR (600 MHz, DMSO-d6) δ 7.87 (s, 1H), 7.80 (dd, J = 1.8 Hz, 1H), 7.61–7.58 (m, 2H), 7.33 (d, J = 8.4 Hz, 1H), 7.29 (d, J = 3.6 Hz, 1H), 7.21–7.18 (m, 2H), 6.84 (d, J = 3.6 Hz, 1H), 5.17 (dd, J = 3.6, 3.0 Hz, 1H), 5.02 (d, J = 6.6 Hz, 1H), 4.57 (d, J = 4.8 Hz, 1H), 4.43–4.39 (m, 3H), 4.22 (s, 2H), 4.02–4.01 (m, 1H), 3.53–3.51 (m, 3H), 3.38–3.37 (m, 1H), 2.35 (s, 3H);

 

13C NMR (101 MHz, DMSO-d6) δ 199.7, 162.6, 160.2, 142.8, 142.1, 140.5, 138.8, 133.3, 130.5, 130.4, 130.4, 129.3, 127.2, 127.0, 127.0, 126.7, 123.5, 116.0, 115.8, 75.2, 72.3, 71.8, 71.3, 63.2, 33.2, 19.2.

 

HRMS (ESI): calcd m/zfor [C24H25FO6S + Na]+ = 483.1248, found m/z 483.1244.

 

 

 

 

 

 

 

Org. Process Res. Dev., Article ASAP

DOI: 10.1021/acs.oprd.7b00281

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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,

Cas 412298-86-3

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

Romaric Gérardy†, Marc Winter‡, Clemens R. Horn‡, Alessandra Vizza‡, Kristof Van Hecke§, and Jean-Christophe M. Monbaliu*† 

† 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

 

*E-mail: jc.monbaliu@ulg.ac.be.

Abstract

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 10

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

PhD Student at Université de Liège

Center for Integrated Technology and Organic Synthesis (CiTOS)

 Université de Liège, Liège Area, Belgium

 

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

Alessandra Vizza

Corning Reactor Technologies, Corning SAS, 7 bis Avenue de Valvins, CS 70156 Samois sur Seine, 77215 Avon Cedex, France

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 R. Horn

Clemens Horn, Senior Research Scientist

Corning SAS

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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.

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.

(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.

 

Position	δC, Type	δH (J in Hz)
1	135.7, C
2	111.3, CH	7.05, d (1.7)
3	147.8, C
4	147.5, C
5	118.1, CH	7.15, d (8.2)
6	119.5, CH	6.95, dd (8.2, 1.7)
7	88.6, CH	5.58, d (5.91)
8	55.7, CH	3.48, m
9	65.1, CH2
a		3.78, m
b		3.85, m
1′	134.9, C
2′	114.7, CH	6.78, s
3′	147.9, C
4′	147.9, C
5′	145.5, C
6′	118.4, CH	6.76, s
7′	33.9, CH2
a		2.96, dd (13.5, 5.0)
b		2.57, dd (13.3, 11.0)
8′	44.0, CH	2.75, 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, CH	7.01, d (1.7)
3″	151.1, C
4″	147.5, C
5″	118.2, CH	7.16, d (8.3)
6″	119.7, CH	6.90, dd (8.2, 1.7)
7″	83.9, CH	4.85, overlap
8″	54.2, CH	2.38, quin (6.9)
9″	60.5, CH2
a		3.88, m
b		3.68, dd (10.9, 6.7)
Glc-1′′′	103.1, CH	4.91, d (7.3)
2′′′	75.1, CH	3.51, m
3′′′	78.5, CH	3.39, m
4′′′	71.6, CH	3.41, m
5′′′	78.4, CH	3.41, m
6′′′	62.6, CH	3.69, overlap
OCH3 (3″)	56.9	3.84, s
OCH3 (3)	56.8	3.88, s
OCH3 (5′)	56.8	3.87, 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.

Figure 2. Key 1H-1H COSY, HMBC (a) and NOESY (b) correlations of 1.

 

 

Molecules2017, 22(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

Abstract:

A new sesquilignan glycoside 1, together with seven known phenolic glycosides 2–8 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 1–8 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

 

 

/////////capselloside, nmr, cosy