2,6-Dihydroxy-4-methylbenzoic Acid

1H NMR

1H NMR (298.2 K, DMSO-d6, 300 MHz, δ in ppm): C 10.87 (br. s, 3 H, H17,12,11), B 6.21 (d, 2 H, J = 0.57 Hz, H14,13), A 2.17 (s, 3 H, H9).

13C NMR

13C NMR (298.2 K, DMSO-d6, 300 MHz, δ in ppm): 9 21.57(C9), 2 98.95 (C2), 1/3 107.98 (C1,3). ), 5 146.29 (C5), 4/6 160.68 (C4,6), 10 172.31 (C10).

In this case study the regioselective enzymatic carboxylation of 3,5-dihydroxytoluene (orcinol) using the nonoxidative 2,3-dihydroxybenzoic acid decarboxylase from Aspergillus oryzae (2,3-DHBD_Ao), followed by an adsorbent-based downstream approach, has been investigated. The product 2,6-dihydroxy-4-methylbenzoic acid (DHMBA) was herein purified by an adsorption–desorption cycle and subsequently obtained with purities >99% without a full elimination of the excess bicarbonate from its reaction solution. Ten adsorbent resins were studied in respect of their ability to recover the product from the reaction solution, whereas the strong anion exchange resin Dowex 1x2 in its chloride form showed affinities >99%, even at bicarbonate concentrations of >3 mol·L–1. Desorption from loaded resin was carried out by a 2 mol·L–1 HCl/acetone mixture, followed by product crystallization during acetone evaporation. This presented concept does not require a final column preparation step and improves the overall atom efficiency of the biocatalytic reaction system.

Org. Process Res. Dev., Article ASAP

DOI: 10.1021/acs.oprd.8b00104

https://pubs.acs.org/doi/suppl/10.1021/acs.oprd.8b00104

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Catalyst-free three-component synthesis of highly functionalized 2,3-dihydropyrroles

Catalyst-free three-component synthesis of highly functionalized 2,3-dihydropyrroles

Dong Wang,a  Linna Li,a  Hairong Feng,a  Hua Sun,a  Fabrice Almeida-Veloso,b  Marine Charavin,b Peng Yua  and  Laurent Désaubry*abc 

 Author affiliations

*Corresponding authors

aSino-French Joint Lab of Food Nutrition/Safety and Medicinal Chemistry, China International Science and Technology Cooperation Base of Food Nutrition/Safety and Medicinal Chemistry, College of Biotechnology, Tianjin University of Science and Technology, Tianjin 300457, China
E-mail: desaubry@unistra.fr

bLaboratory of Therapeutic Innovation (UMR 7200), University of Strasbourg-CNRS, Faculty of Pharmacy, 67400 Illkirch, France

cLaboratory of Biomolecules (UMR7203), Sorbonne University – CNRS, 4 place Jussieu, 75005 Paris, France

Abstract

An efficient synthesis of fully substituted 2,3-dihydropyrroles has been achieved in one step through the three-component reaction of amines, aromatic aldehydes and α-ketoamides. This atom-economical and catalyst-free reaction is highly stereoselective and generates underexplored heterocycles in a single step. These compounds were examined in an enzymatic assay that led to the identification of potent α-glucosidase inhibitors, thereby demonstrating the utility of this novel methodology in medicinal chemistry.

http://pubs.rsc.org/en/Content/ArticleLanding/2018/GC/C8GC00987B?utm_source=feedburner&utm_medium=feed&utm_campaign=Feed%3A+rss%2FGC+%28RSC+-+Green+Chem.+latest+articles%29#!divAbstract

N-(4-Chlorophenyl)-2-oxopropanamide (3a) Cl H N O O 3a Using 4-chloroaniline (1.0 g, 7.8 mmol), in accordance with General Procedure A, the title compound 3a was obtained (810 mg, 52% yield) as a white solid. 1H NMR (400 MHz, CDCl3) δ 8.73 (s, 1H), 7.60 (d, J = 8.0 Hz, 2H), 7.34 (d, J = 8.0 Hz, 2H), 2.57 (s, 3H). 13C NMR (100 MHz, CDCl3) δ 197.1, 157.6, 135.0, 130.6, 129.5, 121.1, 24.2. HRMS (ESI-TOF) m/z calcd. for C9H7NO2Cl- [M-H]- : 196.0171, found 196.0170

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3.4. 1,2,3,4-Tetra-O-Acetyl-β-d-Mannuronic Acid

Laura Beswick

2nd degree connection

PhD Student at Keele University

Gavin J. Miller

2nd degree connection

Lecturer in Organic Chemistry at Keele University

3.4. 1,2,3,4-Tetra-O-Acetyl-β-d-Mannuronic Acid (4)

To a vigorously stirred solution of 1,2,3,4-tetra-O-acetyl-β-d-mannopyranose (3) (1.5 g, 4.30 mmol, 1.0 equiv.) in dichloromethane (20 mL) and water (10 mL) was added (2,2,6,6-tetramethylpiperidin-1-yl)oxyl radical (TEMPO) (336 mg, 2.2 mmol, 0.50 equiv.) and [bis(acetoxy)iodo]benzene (BAIB) (6.9 g, 21.5 mmol, 5.00 equiv.). The solution was stirred at RT for 5 h, whereupon TLC analysis (hexane/ethyl acetate, 1/1) showed complete conversion of starting material to a baseline Rf value spot. The reaction was quenched with aqueous Na2S2O3 solution (10% w/v, 30 mL), the organic layer removed and the aqueous layer acidified to pH 3 using 1M HCl, followed by extraction with ethyl acetate (2 × 30 mL). The organic extracts were combined, dried (MgSO4), filtered and concentrated in vacuo to afford 1,2,3,4-tetra-O-acetyl-β-d-mannuronic acid (4) as a white solid (1.2 g, 3.3 mmol, 75%). Rf = 0.81 (dichloromethane/methanol, 9/1);

 1H-NMR (300 MHz, CDCl3) δH5.96 (1H, d, J = 1.5 Hz, H1), 5.50 (1H, dd, J = 3.2, 1.5 Hz, H2), 5.48 (1H, appt, J = 9.1 Hz, H4), 5.21 (1H, dd, J = 9.1, 3.2 Hz, H3), 4.2 (1H, d, J = 9.1 Hz, H5), 2.21 (3H, s, C(O)CH3), 2.13 (3H, s, C(O)CH3), 2.10 (3H, s, C(O)CH3), 2.04 (3H, s, C(O)CH3).

 13C-NMR (100 MHz, CDCl3) δC 169.9 (C=O), 169.7 (C=O), 169.5 (C=O), 169.4 (C=O), 168.2 (C=O), 89.4 (C1), 72.3 (C5), 69.3 (C3), 66.9 (C2), 65.9 (C4), 20.4 (C(O)CH3), 20.4 (C(O)CH3), 20.3 (C(O)CH3), 20.2 (C(O)CH3); 

FT-HRMS NSI (ES−) m/z Found: (M−H)− 361.0767, C14H17O11 requires 361.0776; FT-IR vmax/cm−1 2986 (O–H), 1751 (C=O).

Molbank 2017, 2017(3), M947; doi:10.3390/M947

Communication

1,2,3,4-Tetra-O-Acetyl-β-d-Mannuronic Acid

Laura Beswick and Gavin J. Miller *

Lennard-Jones Laboratory, School of Chemical and Physical Sciences, Keele University, Keele, Staffordshire ST5 5BG, UK

*

Correspondence: Tel.: +44-1782-734442

Received: 3 July 2017 / Accepted: 11 July 2017 / Published: 14 July 2017

Abstract

: 

1,2,3,4-Tetra-O-acetyl-β-d-mannuronic acid was synthesized in three steps from commercial d-mannose in 21% yield. Regioselective 6-O-tritylation followed by per-acetylation and 6-OTr removal using HBr/AcOH gave the required primary alcohol substrate, which was then oxidised to the target compound using TEMPO/BAIB. None of the synthetic steps required column chromatography and the product was fully characterized by 1H-NMR, 13C-NMR, 2D NMR, MS and IR.

http://www.mdpi.com/1422-8599/2017/3/M947/htm

Keele University, Keele, Staffordshire

Lennard-Jones Laboratory, School of Chemical and Physical Sciences, Keele University,

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“ORGANIC SPECTROSCOPY INT” CATERS TO EDUCATION GLOBALLY, No commercial exploits are done or advertisements added by me. This is a compilation for educational purposes only. P.S. : The views expressed are my personal and in no-way suggest the views of the professional body or the company that I represent

2,4-Diphenyl-2,3-dihydro-1,5-benzothiazepine

2,4-Diphenyl-2,3-dihydro-1,5-benzothiazepine (4a) 1,3-Diphenyl-2-propen-1-one (1a).

Yellow solid; mp 114-116 C [lit.1 , 114-115 °C], AcOEt/PE 1:9.

1H NMR (300 MHz, CDCl3,): 3.07 (t, J = 12.6 Hz, 1 H), 3.32 (dd, J = 4.7, 13.1 Hz, 1 H), 4.99 (dd, J = 4.5, 12.0 Hz, 1 H), 7.12-7.17 (m, 1 H), 7.25-7.30 (m, 5 H), 7.44-7.51 (m, 4 H), 7.62 (d, J = 6.1 Hz, 2 H), 8.06 (d, J = 7.5 Hz, 2 H).

Isolated Yield: 339 mg, 86%

2-(4-Hydroxyphenyl)-4-phenyl-2,3-dihydro-1,5-benzothiazepine (4e) 3-(4-Hydroxyphenyl)-1-phenyl-2-propen-1-one (1e).

Light brown solid; mp 131-134 °C. AcOEt/PE 40:60.

1H NMR (CDCl3, 300 MHz):  = 3.01 (t, J = 12.7 Hz, 1 H), 3.28 (dd, J = 4.8, 12.9 Hz, 1 H), 4.95 (dd, J = 4.7, 12.5 Hz, 1 H), 5.10 (bs, 1 H), 6.76 (d, J = 8.5 Hz, 2 H), 7.18-7.21 (m, 3 H), 7.35 (d, J = 8.5 Hz, 1 H), 7.46- 7.55 (m, 4 H), 7.63 (dd, J =1.5, 7.7 Hz, 1 H), 8.06 (m, 2 H).

13C NMR (CDCl3, 75 MHz): 37.99 (CH2), 60.07 (CH), 115.53 (CH), 123.08 (C), 127.40 (CH), 128.79 (CH), 131.17 (CH), 136.54 (C), 141.59 (C), 155.24 (C). IR (KBr): 1599, 2921, 3350 cm-1 .

MS (ESI): m/z= 332.24 (MH)+ . Anal. Calcd. for C21H17NOS: C, 76.10; H, 5.17; N, 4.23, found: C, 76.21; H, 5.15; N, 4.24. Isolated Yield: 360 mg, 87%

A practical synthesis of 2,3-dihydro-1,5-benzothiazepines

Green Chem., 2017, Accepted Manuscript
DOI: 10.1039/C7GC02097J, Paper

Domenico Carlo Maria Albanese, nicoletta gaggero, Meng Fei
2,3-Dihydro-1,5-benzothiazepines have been obtained through a domino process involving a Michael addition of 2-aminothiophenols to chalcones, followed by in situ cyclization. Up to 98% chemical yields have been obtained at...

A practical synthesis of 2,3-dihydro-1,5-benzothiazepines

 

Domenico Carlo Maria Albanese,  nicoletta gaggero  and  Meng Fei 

Abstract

2,3-Dihydro-1,5-benzothiazepines have been obtained through a domino process involving a Michael addition of 2-aminothiophenols to chalcones, followed by in situ cyclization. Up to 98% chemical yields have been obtained at room temperature under essentially neutral conditions by using hexafluoro-2-propanol as an efficient medium.

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2,3-dihydrobenzo[b][1,4]dioxine

2,3-dihydrobenzo[b][1,4]dioxine

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2,3-Dihydrobenzofuran

• CAS Number 496-16-2
   
• Empirical Formula (Hill Notation) C₈H₈O
   
• Molecular Weight 120.15
•  Beilstein Registry Number 111928
   

http://www.rsc.org/suppdata/gc/c4/c4gc01822b/c4gc01822b1.pdfhttp://www.rsc.org/suppdata/gc/c4/c4gc01822b/c4gc01822b1.pdf


1H NMR

MASS

IR

UV

1H NMRPREDICT

13C NMR PREDICT

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2,5-Diformylfuran an easy molecule to learn NMR

2,5-Diformylfuran (DFF), 5 (lit. 2 ) 2 Kashparova, V. P., Khokhlova, E. A., Galkin, K. I., Chernyshev, V. M. & Ananikov, V. P. The “onepot” synthesis of 2,5-diformylfuran, a promising synthon for organic materials in the conversion of biomass. Russ. Chem. Bull. 64, 1069-1073 (2015).

1H NMR (CDCl3) = 9.87 (s, 2H), 7.35 (s, 2H);

13C NMR (CDCl3) = 181.1, 154.1, 122.5 ppm.

PREDICT

Efficient route for the construction of polycyclic systems from bioderived HMF 

Green Chem., 2017, Advance Article
DOI: 10.1039/C7GC02211E, Paper

F. A. Kucherov, K. I. Galkin, E. G. Gordeev, V. P. Ananikov
Efficient one-pot synthesis of tricyclic compounds from biobased 5-hydroxymethylfurfural (HMF) is described using a [4 + 2] cycloaddition reaction.

Efficient route for the construction of polycyclic systems from bioderived HMF

F. A. Kucherov,^a  K. I. Galkin,^a  E. G. Gordeev^a  and  V. P. Ananikov*^a 

 Author affiliations

*Corresponding authors

^aZelinsky Institute of Organic Chemistry, Russian Academy of Sciences, Leninsky pr. 47, Moscow 119991, Russia
E-mail: val@ioc.ac.ru
Web: http://AnanikovLab.ru

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2,5-Bis(morpholinomethyl)furan

2,5-Bis(morpholinomethyl)furan, 11

Yield 98%, 1H NMR (CDCl3) = 6.13 (s, 2H), 3.70 (m, 8H), 3.51 (s, 4H), 2.45 (m, 8H);

13C NMR (CDCl3) = 150.9, 109.7, 66.8, 55.3, 53.2 ppm.

 m/z HRMS (ESI) Calcd. for C14H22N2O3 [M+H]: 267.1703. Found 267.1703.

Efficient route for the construction of polycyclic systems from bioderived HMF 

Green Chem., 2017, Advance Article
DOI: 10.1039/C7GC02211E, Paper

F. A. Kucherov, K. I. Galkin, E. G. Gordeev, V. P. Ananikov
Efficient one-pot synthesis of tricyclic compounds from biobased 5-hydroxymethylfurfural (HMF) is described using a [4 + 2] cycloaddition reaction.

Efficient route for the construction of polycyclic systems from bioderived HMF

F. A. Kucherov,^a  K. I. Galkin,^a  E. G. Gordeev^a  and  V. P. Ananikov*^a 

 Author affiliations

*Corresponding authors

^aZelinsky Institute of Organic Chemistry, Russian Academy of Sciences, Leninsky pr. 47, Moscow 119991, Russia
E-mail: val@ioc.ac.ru
Web: http://AnanikovLab.ru

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