AUTHOR OF THIS BLOG

DR ANTHONY MELVIN CRASTO, WORLDDRUGTRACKER
Nov 092017
 

Zhong-Xia WANG

STR1

 

STR1

N,N-dimethyl-4-biphenylamine

Molecular Formula, C14H15N
Molecular Weight, 197.28
CAS Number, 1137-79-7

(1) N,N-dimethyl-[1,1′-biphenyl]-4-amine (3a) 5,6

Elute: EtOAc/petroleum ether: 1/100 (v/v), white solid, yield 97.8 mg (99%).

1H NMR (400 MHz, CDCl3): δ 7.56 (d, J = 7.8 Hz, 2H), 7.51 (d, J = 8.8 Hz, 2H), 7.40 (t, J = 7.7 Hz, 2H), 7.30–7.21 (m, 1H), 6.81 (d, J = 8.8 Hz, 2H), 3.00 (s, 6H).

13C NMR (101 MHz, CDCl3): δ 150.09, 141.34, 129.37, 128.78, 127.84, 126.43, 126.12, 112.90, 40.97.

5 Yang, X.; Wang, Z.-X. Organometallics 2014, 33, 5863.

(6) Stibingerova, I.; Voltrova, S.; Kocova, S.; Lindale, M.; Srogl, J. Org. Lett. 2016, 18, 312.

STR1 STR2

 

Transition-Metal-Free Cross-Coupling of Aryl and Heteroaryl Thiols with Arylzinc Reagents

Bo Yang and Zhong-Xia Wang* 
 CAS Key Laboratory of Soft Matter Chemistry, Hefei National Laboratory for Physical Sciences at Microscale and Department of Chemistry, University of Science and Technology of China, Hefei, Anhui 230026, P. R. China
 Collaborative Innovation Center of Chemical Science and Engineering (Tianjin), Tianjin 300072, P. R. China
Org. Lett., Article ASAP
DOI: 10.1021/acs.orglett.7b03145

Abstract

Abstract Image

Cross-coupling of (hetero)arylthiols with arylzinc reagents via C–S cleavage was performed under transition-metal-free conditions. The reaction displays a wide scope of substrates and high functional-group tolerance. Electron-rich and -deficient (hetero)arylthiols and arylzinc reagents can be employed in this transformation. Mg2+ and Li+ ions were demonstrated to facilitate the reaction.

In summary, we developed a transition-metal-free coupling reaction of (hetero)arylthiols with arylzinc reagents to form bi(hetero)aryls. The reaction exhibited wide substrate scope and good compatibility of functional groups. Electron-rich and -poor aryl or heteroaryl thiols can be converted. Various arylzinc reagents, including electron-rich and electron-poor reagents, can be employed as the coupling partners. Preliminary mechanistic studies suggest a nucleophilic aromatic substitution pathway, and Mg2+ and Li+ ions play important roles in the process of reaction. This study provides an example of S2– as a leaving group in an aromatic system and an effective methodology for the synthesis of bi(hetero)aryls including pharmaceutical molecules without transition-metal impurities.

Zhong-Xia WANG

Department: Department of Chemistry
Mailing Address:
Department of Chemistry, University of Science and Technology of China, 96 Jinzhai Rd, Hefei, Anhui, 230026, PR China
Postal Code:
230026
Phone:
+86-551-63603043
Fax:
Homepage:
http://chem.ustc.edu.cn/szdw_16/bd/201210/t20121023_142877.html
Zhong-Xia Wang is a professor in the Department of Chemistry at the University of Science and Technology 
of China. He received his BS degree (1983) and MS degree (1986) from Nankai University, 
and PhD degree (1997) from the University of Sussex, UK. Since July 1986, Wang has been working 
at the University of Science and Technology of China (USTC) successively as Assistant, 
Lecturer, Associate Professor, and Professor. From Aug. 1993 to Oct. 1996, he pursued his doctoral 
studies at the University of Sussex, UK, and from Oct. 1999 to Oct. 2000, he was a Research Associate 
at the Chinese University of Hong Kong.

 学 系
Department of Chemistry

Predicts

STR1

STR1

////////////

http://pubs.acs.org/doi/10.1021/acs.orglett.7b03145

 

“ALL FOR DRUGS” 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

Follow amcrasto on Twitter

Share
Nov 032017
 

Image result for Kalpana C. Maheria sv

1-benzyl-2, 4, 5-triphenyl-1H-imidazole

STR1 STR2 str3

. 1-Benzyl-2,4,5-triphenyl-1H-imidazole (5a, n = 1).

Off-white solid; m.p.: 160–162 °C;

anal. calcd. for C28H22N2: C, 87.01, H, 5.74, N, 7.25%. Found: C, 87.13, H, 5.70, N, 7.19%;

UV (λmax, ethanol) = 280 nm;

FT-IR (KBr, cm−1 ): 3060 (C–H stretch), 3031, 1600 (CN), 1497, 1483, 1447 (CC), 1352 (C–N stretch), 769, 697 (C–H band);

1 H NMR (400 MHz, DMSO): 5.16 (s, 2H, CH2), 6.74–7.67 (m, 20H, Ar–H) ppm;

13C NMR (100 MHz, DMSO): 47.6 (CH2, C8), 125.1 (CHarom, C28), 126.0 (CHarom, C26), 126.2 (CHarom, C30), 126.4 (CHarom, C11), 127.0 (CHarom, C15), 127.1 (CHarom, C16), 127.7 (CHarom, C20), 128.0 (CHarom, C21), 128.1 (CHarom, C25), 128.4 (CHarom, C13), 128.5 (CHarom, C18), 128.6 (CHarom, C27), 128.8 (C1), 128.8 (CHarom, C12), 128.9 (CHarom, C14), 130.1 (CHarom, C17), 130.3 (CHarom, C19), 130.5 (CHarom, C22), 130.7 (CHarom, C24), 131.0 (CHarom, C29), 134.4 (CHarom, C9), 135.1 (CHarom, C23), 136.8 (CHarom, C7), 137.0 (CHarom, C10), 137.2 (CHarom, C6), 145.4 (C2), 147.0 (C4) ppm;

MS: m/z = 387.5 (M + H)+

An efficient green protocol for the synthesis of tetra-substituted imidazoles catalyzed by zeolite BEA: effect of surface acidity and polarity of zeolite

*Corresponding authors

Abstract

In the present study, the catalytic activity of various medium (H-ZSM-5) and large pore (H-BEA, H-Y, H-MOR) zeolites were studied as solid acid catalysts. The zeolite H-BEA is found to be an efficient catalyst for the synthesis of 1-benzyl-2,4,5-triphenyl-1H-imidazoles through one-pot, 4-component reaction (4-CR) between benzil, NH4OAc, substituted aromatic aldehydes and benzyl amine. The hydrophobicity, Si/Al ratio and acidic properties of zeolite BEA were well improved by controlled dealumination. The synthesized materials were characterized by various characterization techniques such as XRD, ICP-OES, BET, NH3-TPD, FT-IR, pyridine FT-IR, 27Al and 1H MAS NMR. It has been observed that the dealumination of the parent zeolite H-BEA (12) results in the enhanced strength of Brønsted acidity up to a certain Si/Al ratio which is attributed to the inductive effect of Lewis acidic EFAl species, leading to the higher activity of the zeolite BEA (15) catalyst towards the synthesis of 1-benzyl-2,4,5-triphenyl-1H-imidazoles under thermal solvent-free conditions with good to excellent yields. Using the present catalytic synthetic protocol, diverse tetra-substituted imidazoles, which are among the significant biologically active scaffolds, were synthesized in high yield within a shorter reaction time. The effect of polarity, surface acidity and extra framework Al species of the catalysts has been well demonstrated by means of pyridine FT-IR, and 27Al and 1H MAS NMR. The solvent-free synthetic protocol makes the process environmentally benign and economically viable.

Graphical abstract: An efficient green protocol for the synthesis of tetra-substituted imidazoles catalyzed by zeolite BEA: effect of surface acidity and polarity of zeolite
STR1
STR1
Image result for S. V. National Institute of Technology, Ichchhanath, Surat
Image result for S. V. National Institute of Technology, Ichchhanath, Surat
Image result for S. V. National Institute of Technology, Ichchhanath, Surat
S. V. National Institute of Technology, Ichchhanath, Surat
Image result for Mandvi Science College, Mandvi – 394160, Surat, India
Image result for Mandvi Science College, Mandvi – 394160, Surat, India
Mandvi Science College, Mandvi – 394160, Surat, India

////////

DISCLAIMER

“ALL FOR DRUGS” 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
Share

Towards nitrile-substituted cyclopropanes – a slow-release protocol for safe and scalable applications of diazo acetonitrile

 spectroscopy, SYNTHESIS  Comments Off on Towards nitrile-substituted cyclopropanes – a slow-release protocol for safe and scalable applications of diazo acetonitrile
Apr 222017
 

Towards nitrile-substituted cyclopropanes – a slow-release protocol for safe and scalable applications of diazo acetonitrile

 Green Chem., 2017, Advance Article
DOI: 10.1039/C7GC00602K, Communication
Katharina J. Hock, Robin Spitzner, Rene M. Koenigs
Applications of diazo acetonitrile in cyclopropa(e)nation reactions are realized in a slow-release protocol with bench-stable reagents. Cyclopropyl nitriles are obtained in one step in good diastereoselectivity on a gram-scale providing an efficient entry into this class of fragrances and drug-like molecules.
STR1
STR2
trans-2-phenylcyclopropane-1-carbonitrile
colorless solid (46 mg, 81%);
m.p. = 29°C;
1 H-NMR (600 MHz, CDCl3): δ = 7.34 – 7.30 (m, 2H), 7.28 – 7.24 (m, 1H), 7.12 – 7.08 (m, 2H), 2.63 (ddd, J = 9.2, 6.7, 4.7 Hz, 1H), 1.62 (dt, J = 9.2, 5.4 Hz, 1H), 1.55 (ddd, J = 8.7, 5.5, 4.8 Hz, 1H), 1.45 (ddd, J = 8.8, 6.7, 5.3 Hz, 1H);
13C-NMR (151 MHz, CDCl3): δ = 137.55, 128.76, 127.41, 126.31, 121.05, 24.90, 15.24, 6.63;
HRMS (ESI): m/z calc. for [C10H9NNa]: 166.06272, found 166.06276;
IR (KBr): νmax/cm-1 = 3044, 2235, 2098, 1761, 1600, 1461, 1220, 1051, 920, 705.
The analytical data is in correspondence with the literature [2]
STR1 STR2
[2] M. Gao, N. N. Patwardhan, P. R. Carlier, J. Am. Chem. Soc., 2013, 135 (38), 14390–14400

Towards nitrile-substituted cyclopropanes – a slow-release protocol for safe and scalable applications of diazo acetonitrile

Author affiliations

Abstract

Diazo acetonitrile has long been neglected despite its high value in organic synthesis due to a high risk of explosions. Herein, we report our efforts towards the transient and safe generation of this diazo compound, its applications in iron catalyzed cyclopropanation and cyclopropenation reactions and the gram-scale synthesis of cyclopropyl nitriles.

Graphical abstract: Towards nitrile-substituted cyclopropanes – a slow-release protocol for safe and scalable applications of diazo acetonitrile
//////////
Share

(3R)-4-[2-chloro-6-[[(R)-methylsulfinyl]methyl]pyrimidin-4-yl]-3-methyl-morpholine

 spectroscopy  Comments Off on (3R)-4-[2-chloro-6-[[(R)-methylsulfinyl]methyl]pyrimidin-4-yl]-3-methyl-morpholine
Feb 092017
 

STR1

 

(3R)-4-[2-chloro-6-[[(R)-methylsulfinyl]methyl]pyrimidin-4-yl]-3-methyl-morpholine

STR1 STR2

Synthesis of (3R)-4-[2-chloro-6-[[(R)-methylsulfinyl]methyl]pyrimidin-4-yl]-3-methyl-morpholine (10)

off-white solid (53.9 kg, 68.3% yield). 1H NMR (400 MHz, DMSO-d6, δ): 1.20 (d, J = 6.8 Hz, 3 H), 2.52 (m, 1 H), 2.63 (s, 3 H), 3.21 (m, 1 H), 3.44 (m, 1 H), 3.58 (dd, J = 11.6, 3.1 Hz, 1 H), 3.72 (d, J = 11.5 Hz, 1 H), 3.92 (m, 3 H), 4.07 (d, J = 12.4 Hz, 1 H), 6.80 (s, 1 H); Assay (HPLC) 99%; Assay (QNMR) 100%; Chiral purity (HPLC) (R,R)-diastereoisomer 99.6%, (R,S)-diastereoisomer 0.4%.

 

Abstract Image

A Baeyer–Villiger monooxygenase enzyme has been used to manufacture a chiral sulfoxide drug intermediate on a kilogram scale. This paper describes the evolution of the biocatalytic manufacturing process from the initial enzyme screen, development of a kilo lab process, to further optimization for plant scale manufacture. Efficient gas–liquid mass transfer of oxygen is key to obtaining a high yield.

Development and Scale-up of a Biocatalytic Process To Form a Chiral Sulfoxide

The Departments of Pharmaceutical Sciences and Pharmaceutical Technology and Development, AstraZeneca, Silk Road Business Park, Macclesfield, Cheshire SK10 2NA, United Kingdom
Org. Process Res. Dev., Article ASAP
DOI: 10.1021/acs.oprd.6b00391
Publication Date (Web): January 4, 2017
Copyright © 2017 American Chemical Society
*Tel: +44 (0)1625-519149. E-mail: william.goundry@astrazeneca.com.
Figure
Examples of biologically active molecules containing a sulfoxide or sulfoximine: esomeprazole (3), aprikalim (4), oxisurane (5), OPC-29030 (6), ZD3638 (7), buthionine sulfoximine (8), and AZD6738 (9).

“ALL FOR DRUGS” CATERS TO EDUCATION GLOBALLY, No commercial exploits are done or advertisements added by me. This article 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

Share

(±)-trans-ethyl 2-(3,4-difluorophenyl)Cyclopropanecarboxylate

 spectroscopy  Comments Off on (±)-trans-ethyl 2-(3,4-difluorophenyl)Cyclopropanecarboxylate
Feb 092017
 

STR1 STR2 STR3

(±)-trans-ethyl 2-(3,4-difluorophenyl)Cyclopropanecarboxylate

C12H12F2O2

GC-MS (EI) m/z: [M]+ calc. for C12H12F2O2 + : 226.08; found: 226.08.

δH (400 MHz, CDCl3): 1.25 (1H, ddd, 3 J 8.4 Hz, 3 J 6.4 Hz, 2 J 4.5 Hz , 3-H); 1.28 (3H, t 3 J 6.4 Hz CH3Ethyl) 1.57-1.62 (2H, m, 3 J 9.2 Hz, 3 J 5.2 Hz, 2 J 4.5 Hz, 3-H + H2O), 1.84 (1H, ddd, 3 J 8.5 Hz, 3 J 5.3 Hz, 3 J 4.3 Hz , 2-H), 2.47 (1H, ddd, 3 J 9.5 Hz, 3 J 6.4 Hz, 3 J 4.2 Hz , 1-H), 4.17 (2H, q, 3 J 6.3 Hz, CH2Ethyl) 6.81-6.87 (1H, m, 3 J 8.5 Hz, 4 J 7.6 Hz, 4 J 2.4 Hz, 6-H’ ), 6.88 (1H, ddd, 3 J 11.5 Hz, 4 J 7.6 Hz, 4 J 2.2 Hz, 2-H’) 7.06 (1H, dt, 3 J 10.3 Hz, 3 J 8.2 Hz. 5-H’).

δc (400 MHz, CDCl3): 14.27 (CH3Ethyl), 16.84 (3-C) 24.04 (1-C), 25.14 (d, 4 J 1.4, 2-C), 60.71 (CH2Ethyl), 114.74 (d, 2 J 19 Hz, 2-C’), 117.09 (d, 2 J 18 Hz, 5-C’), 122.25 (dd, 3 J 6.1 Hz, 4 J 3.4 Hz, 6- C’), 137.06 (dd, 3 J 6.1 Hz, 4 J 3.4 Hz, 1- C’), 149.2 (dd, 1 J 248 Hz, 2 J 13 Hz, 4-C’) 151.32 (dd, 1 J 249 Hz, 2 J 12.5 Hz, 3-C’) 172.87 (Ccarbonyl).

[ ] 20 a D = -381.9 (c 1.0 in EtOH) for (1R,2R)-3, ee = 95%

Abstract Image

In this study a batch reactor process is compared to a flow chemistry approach for lipase-catalyzed resolution of the cyclopropanecarboxylate ester (±)-3. (1R,2R)-3 is a precursor of the amine (1R,2S)-2 which is a key building block of the API ticagrelor. For both flow and batch operation, the biocatalyst could be recycled several times, whereas in the case of the flow process the reaction time was significantly reduced.

Comparison of a Batch and Flow Approach for the Lipase-Catalyzed Resolution of a Cyclopropanecarboxylate Ester, A Key Building Block for the Synthesis of Ticagrelor

School of Chemistry, University of Manchester, Manchester Institute of Biotechnology, 131 Princess Street, Manchester M1 7DN, United Kingdom
Chemessentia, SRL – Via G. Bovio, 6-28100 Novara, Italy
§ Institute of Process Research and Development, School of Chemistry, University of Leeds, Woodhouse Lane, Leeds, LS2 9JT, United Kingdom
Org. Process Res. Dev., Article ASAP
DOI: 10.1021/acs.oprd.6b00346
Publication Date (Web): December 22, 2016
Copyright © 2016 American Chemical Society

“ALL FOR DRUGS” CATERS TO EDUCATION GLOBALLY, No commercial exploits are done or advertisements added by me. This article 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

Share

2,2′-(1-(tert-Butoxycarbonyl)pyrrolidine-3,4-diyl)diacetic Acid

 spectroscopy, SYNTHESIS, Uncategorized  Comments Off on 2,2′-(1-(tert-Butoxycarbonyl)pyrrolidine-3,4-diyl)diacetic Acid
Feb 012017
 

 

STR1

2,2′-(1-(tert-Butoxycarbonyl)pyrrolidine-3,4-diyl)diacetic Acid

STR1 STR2 STR3 str4 str5

2,2′-(1-(tert-Butoxycarbonyl)pyrrolidine-3,4-diyl)diacetic Acid 

as a white solid. Mp: 162–163 °C, % purity: 94.09% (HPLC);
1H NMR (DMSO-d6, 400 MHz) δ: 1.38 (s, 9H), 2.10–2.18 (m, 2H), 2.28–2.32 (m, 2H), 2.49–2.50 (m, 2H, merged with DMSO peak), 2.97–3.03 (m, 2H), 3.33–3.40 (m, 2H), 12.23 (bs, 2H); 1H NMR (CD3OD, 400 MHz) δ: 1.46 (s, 9H), 2.26 (ddd, J1 = 2.8 Hz, J2 = 9.2 Hz, J3 = 16.0 Hz, 2H), 2.43 (dd, J1 = 5.2 Hz, J2 = 16.0 Hz, 2H), 2.69 (m, 2H), 3.16 (dd, J1 = 5.2 Hz, J2 = 10.8 Hz, 2H), 3.49–3.54 (m, 2H);
13C NMR (DMSO-d6, 100 MHz) δ: 28.49, 32.97, 36.49, 37.31, 50.10, 50.20, 78.67, 154.05, 173.96;
IR (KBr): ν = 871, 933, 1143, 1166, 1292, 1411, 1689, 1708, 2881, 2929, 2980, 3001 cm–1;
TOFMS: [C13H21NO6 – H+]: calculated 286.1296, found 286.1031(100%).
HPLC conditions were as follows for compound ; Agilent 1100 series, column: YMC J’SPHERE C18 (150 mm X 4.6 mm) 4µm with mobile phases A (0.05% TFA in water) and B (acetonitrile). Detection was at 210 nm, flow was set at 1.0 mL/min, and the temperature was 30 °C (Run time: 45 min). Gradient: 0 min, A = 90%, B = 10%; 5.0 min, A = 90%, B = 10%; 25 min, A = 0%, B = 100%; 30 min, A = 0%, B = 100%, 35 min, A = 90%, B = 10%; 45 min, A = 90%, B = 10%.
Org. Process Res. Dev., Article ASAP
DOI: 10.1021/acs.oprd.6b00399
/////////
Share

Dimethyl 4,4′-(Benzylazanediyl)(2E,2′E)-bis(but-2-enoate)

 spectroscopy, SYNTHESIS, Uncategorized  Comments Off on Dimethyl 4,4′-(Benzylazanediyl)(2E,2′E)-bis(but-2-enoate)
Jan 312017
 

str5

Dimethyl 4,4′-(Benzylazanediyl)(2E,2′E)-bis(but-2-enoate)

STR1

IR (CHCl3): ν = 758, 1215, 1278, 1437, 1660, 1720, 2806, 2953, 3020, 3421 cm–1;

 

STR2

13C NMR (CDCl3, 100 MHz) δ: 51.53, 53.42, 58.37, 122.66, 127.28, 128.41, 128.55, 128.76, 138.24, 145.84, 166.58;

 

STR3

1H NMR (CDCl3, 400 MHz) δ: 3.23 (dd, J1 = 1.6 Hz, J2 = 6.0 Hz, 4H), 3.62 (s, 2H), 3.75 (s, 6H), 6.07 (dt, J1 = 1.6 Hz, J2 = 16.0 Hz, 2H), 6.97 (dt, J1 = 6.0 Hz, J2 = 16.0 Hz, 2H), 7.25–7.34 (m, 5H-merged with CDCl3 proton);

 

str4

TOFMS: [C17H21NO4 + H+]: calculated 304.1543, found 304.1703(100%).

str5

 

UPLC conditions were as follows for compound 11; Acquity Waters, column: BEH C18 (2.1 mm X 100 mm) 1.7 µm with mobile phases A (0.05% TFA in water) and B (acetonitrile). Detection was at 220 nm, flow was set at 0.4 mL/min, and the temperature was 30 °C (Run time: 9 min). Gradient: 0 min, A = 90%, B = 10%; 0.5 min, A = 90%, B = 10%; 6.0 min, A = 0%, B = 100%; 7.5 min, A = 0%, B = 100%; 7.6 min, A = 90%, B = 10%; 9.0 min, A = 90%, B = 10%.

 

Dimethyl 4,4′-(Benzylazanediyl)(2E,2′E)-bis(but-2-enoate) (11)

as a yellow oil. % purity: 93.4% (UPLC);
1H NMR (CDCl3, 400 MHz) δ: 3.23 (dd, J1 = 1.6 Hz, J2 = 6.0 Hz, 4H), 3.62 (s, 2H), 3.75 (s, 6H), 6.07 (dt, J1 = 1.6 Hz, J2 = 16.0 Hz, 2H), 6.97 (dt, J1 = 6.0 Hz, J2 = 16.0 Hz, 2H), 7.25–7.34 (m, 5H-merged with CDCl3 proton);
13C NMR (CDCl3, 100 MHz) δ: 51.53, 53.42, 58.37, 122.66, 127.28, 128.41, 128.55, 128.76, 138.24, 145.84, 166.58;
IR (CHCl3): ν = 758, 1215, 1278, 1437, 1660, 1720, 2806, 2953, 3020, 3421 cm–1;
TOFMS: [C17H21NO4 + H+]: calculated 304.1543, found 304.1703(100%).
Org. Process Res. Dev., Article ASAP
DOI: 10.1021/acs.oprd.6b00399
//////
Share

1-Bromo-4-fluoro-2-((2-iodobenzyl)oxy)benzene

 Uncategorized  Comments Off on 1-Bromo-4-fluoro-2-((2-iodobenzyl)oxy)benzene
Jan 252017
 

STR1

1-Bromo-4-fluoro-2-((2-iodobenzyl)oxy)benzene

CAS 1161931-51-6

STR1 STR2

Mp 89.8–92.3 °C.

IR (neat, ATR): 3072 (w), 1482 (s), 1451 (s), 1294 (s), 1294 (s) cm–1.

1H NMR (399 MHz, DMSO-d6) δ 5.12 (s, 2H), 6.81 (td, J = 8.49, 2.77 Hz, 1H), 7.14 (td, J = 7.64, 1.65 Hz, 1H), 7.18 (dd, J = 10.90, 2.82 Hz, 1H), 7.46 (td, J = 7.52, 0.92 Hz, 1H), 7.60 (dd, J = 7.64, 1.41 Hz, 1H), 7.62 (dd, J = 8.66, 6.23 Hz, 1H), 7.92 (dd, J = 7.83, 0.83 Hz, 1H).

13C NMR (100 MHz, DMSO-d6) δ 74.5, 99.2, 102.4 (d, J = 27.1 Hz), 105.8 (d, J = 3.4 Hz), 108.9 (d, J = 22.5 Hz), 128.5, 129.8, 130.3, 133.6 (d, J = 9.9 Hz), 138.0, 139.2, 155.4 (d, J = 10.7 Hz), 162.2 (d, J = 244.3 Hz).

GCMS: m/z [M]+ calcd for C13H9BrFIO: 405.88600; found: 405.88620.

1H AND 13C NMR PREDICT

STR1 STR2 STR3 str4

 

Org. Process Res. Dev., Article ASAP

“ALL FOR DRUGS” CATERS TO EDUCATION GLOBALLY, No commercial exploits are done or advertisements added by me. This article 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

////////////
Brc2ccc(F)cc2OCc1ccccc1I
Share

Synthesis of (E)-2,4-Dinitro-N-((2E,4E)-4-phenyl-5-(pyrrolidin-1-yl)penta-2,4-dienylidene)aniline

 spectroscopy, SYNTHESIS, Uncategorized  Comments Off on Synthesis of (E)-2,4-Dinitro-N-((2E,4E)-4-phenyl-5-(pyrrolidin-1-yl)penta-2,4-dienylidene)aniline
Dec 212016
 

str1

Cas 1204588-48-6
MF C21 H20 N4 O4
MW 392.41
Benzenamine, 2,​4-​dinitro-​N-​[(2E,​4E)​-​4-​phenyl-​5-​(1-​pyrrolidinyl)​-​2,​4-​pentadien-​1-​ylidene]​-​, [N(E)​]​-
(E)-2,4-Dinitro-N-((2E,4E)-4-phenyl-5-(pyrrolidin-1-yl)penta-2,4-dienylidene)aniline
str1

 

 

Molbank 2009, 2009(3), M604; doi:10.3390/M604

Synthesis of (E)-2,4-Dinitro-N-((2E,4E)-4-phenyl-5-(pyrrolidin-1-yl)penta-2,4-dienylidene)aniline
Nosratollah Mahmoodi 1,*, Manuchehr Mamaghani 1, Ali Ghanadzadeh 2, Majid Arvand 3 and Mostafa Fesanghari 1
1Laboratory of Organic Chemistry, Faculty of Science, University of Guilan, P.O.Box 1914, Rasht, Iran,
2Departments of Physical Chemistry, Faculty of Science, University of Guilan, P.O.Box 1914, Rasht, Iran
3Departments of Analytical Chemistry, Faculty of Science, University of Guilan, P.O.Box 1914, Rasht, Iran
*Author to whom correspondence should be addressed
mahmoodi@guilan.ac.ir, m-chem41@guilan.ac.ir, aggilani@guilan.ac.ir, arvand@guilan.ac.ir, nosmahmoodi@gmail.com

Abstract:

(E)-2,4-Dinitro-N-((2E,4E)-4-phenyl-5-(pyrrolidin-1-yl)penta-2,4-dienylidene) aniline dye was prepared in one pot by reaction of premade N-2,4-dinitrophenyl-3-phenylpyridinium chloride (DNPPC) and pyrrolidine in absolute MeOH.
Keywords:

N-2,4-dinitrophenyl-3-phenylpyridinium chloride (DNPPC); photochromic; pyridinium salt

N-2,4-Dinitrophenyl-3-phenylpyridinium chloride (DNPPC) 1 was prepared according to the literature method [1,2,3,4,5,6,7]. Recently, we became interested in the synthesis of photochromic compounds [8,9,10]. The UV-Vis spectra under irradiation of UV light of dye 2 indicate photochromic properties for this molecule. The salt 1 was premade and typically isolated and purified by recrystallization and characterized. To a solution of 1-chloro-2,4-dinitrobenzene (1.42 g, 7.01 mmol) in acetone (10 mL) was added 3-phenylpyridine (1.0 mL, 6.97 mmol). The reaction was heated at reflux for 48 h. The solvent was removed under reduced pressure and the red residue was stirred in hexanes. The precipitated product was collected by vacuum filtration to afford pure pyridinium salt 1 as a reddish brown solid (2.23 g, 6.25 mmol, 90%). 1H NMR (CDCl3, 500 MHz): δ (ppm) 9.9 (s, 1H), 9.4 (d, J = 6.0 Hz, 1H), 9.3 (d, J = 8.3 Hz, 1H), 9.2 (d, J = 2.2 Hz, 1H), 9.0 (dd, J = 8.7, 2.4 Hz, 1H), 8.5-8.6 (m, 2H), 8.0 (d, J = 7.3 Hz, 2H), 7.6- 7.7 (m, 3H); 13C NMR (CDCl3, 125 MHz): δ (ppm) 149.2, 145.6, 144.3, 144.2, 143.0, 139.2, 138.7, 132.5, 132.3, 130.6, 130.2, 129.6, 128.0, 127.6, 121.3; IR (KBr pellet) 3202, 3129, 2994, 2901, 1609 cm-1; m. p. = 182-183 °C; HRMS m/z Calcd for C17H12N3O4+ (M)+ 322.0828, found 322.0836.
Molbank 2009 m604 i001
Reaction of pyrrolidine with salt (1) leads to the opening of the pyridinium ring and formation of dye 2. This dye was prepared from reaction of salt 1 (0.5 g, 1.4 mmol) in 5 mL absolute MeOH after cooling a reaction mixture to -10oC and keeping at this temperature for 15 min. To this was added pyrrolidine (0.1 g, 1.4 mmol) in 3 mL absolute MeOH over a period of 10 min. The prepared solid was filtered, washed with CH2Cl2, dried and recrystallized from n-hexane to yield 68% (0.37 g, 0.95 mmol) of pure metallic greenish-brown 2,
m.p. = 146 oC.
IR (KBr): 3040, 2950, 1616, 1514, 1492, 1469, 1321, 1215, 1170, 1105, 956, 904, 862, 727 cm-1.
1H NMR (500 MHz, CDCl3): δ (ppm) 8.7 (d, J = 2.4 Hz, 1H) 8.3 (dd, J = 2.4, 8.84 Hz, 1H), 8.0 (s, 1H), 7.5 (d, J = 7.4 Hz, 2H), 7.4-7.5 (t, J = 7.5 Hz, 2H), 7.3-7.4 (m, 1H), 7.2 (d, J = 12.5 Hz, 1H), 7.1 (d, J = 8.9 Hz, 1H), 7.0 (d, J = 12.1 Hz, 1H), 5.4 (t, J = 12.2 Hz, 1H), 3.3 (br, 4H), 2.0 (br, 4H);
13C NMR (125 MHz, CDCl3): δ (ppm) 22.0, 55.6, 114.7, 117.4, 120.0, 124.1, 126.4, 128.7, 128,8, 129.0, 132.7, 137.1, 137.3, 142.9, 147.8, 150.2, 163.8.
Anal. Calcd for C21H20N4O4: %C = 64.28, %H = 5.14, %N = 14.28. Found: %C = 64.08, %H = 5.11, %N = 14.07.

str1

 

 

1H NMR PREDICT

str0

ACTUAL….

1H NMR (500 MHz, CDCl3): δ (ppm) 8.7 (d, J = 2.4 Hz, 1H) 8.3 (dd, J = 2.4, 8.84 Hz, 1H), 8.0 (s, 1H), 7.5 (d, J = 7.4 Hz, 2H), 7.4-7.5 (t, J = 7.5 Hz, 2H), 7.3-7.4 (m, 1H), 7.2 (d, J = 12.5 Hz, 1H), 7.1 (d, J = 8.9 Hz, 1H), 7.0 (d, J = 12.1 Hz, 1H), 5.4 (t, J = 12.2 Hz, 1H), 3.3 (br, 4H), 2.0 (br, 4H);

str0

 

13 C NMR PREDICT

 

str1

ACTUAL…….13C NMR (125 MHz, CDCl3): δ (ppm) 22.0, 55.6, 114.7, 117.4, 120.0, 124.1, 126.4, 128.7, 128,8, 129.0, 132.7, 137.1, 137.3, 142.9, 147.8, 150.2, 163.8.

str3

////////////Synthesis, (E)-2,4-Dinitro-N-((2E,4E)-4-phenyl-5-(pyrrolidin-1-yl)penta-2,4-dienylidene)aniline

[O-][N+](=O)c3ccc(\N=C\C=C\C(=C/N1CCCC1)c2ccccc2)c([N+]([O-])=O)c3

Share

NMR, 3-[3-(benzoylamino)-4-hydroxylphenyl] propanoic acid

 spectroscopy  Comments Off on NMR, 3-[3-(benzoylamino)-4-hydroxylphenyl] propanoic acid
Jul 022015
 

 

 

http://www.google.com/patents/WO2008022462A1?cl=en

 

1 H-NMR Spectrum of Compound 35…………3-[3-(benzoylamino)-4-hydroxylphenyl] propanoic acid

1H-NMR (Acetone-D6) δ: 2.60 (t, 2H, J = 7.4, H- 3), 2.84 (t, 2H, J = 7.9, H-2), 6.89 (d, IH, J = 8.2, H-8), 7.00 (dd, IH, J = 2.1 , 8.25, H- 9), 7.57 (m, 4H, H-5, H-4′, H-5′, H-61), 8.05 (d, 2H, J = 8.2, H-3′, H-7′), 9.07 (broad s, IH, NH), 9.54 (broad s, IH, OH), 10.58 (broad s, IH, CO2H).

Figure imgf000063_0001
Figure imgf000063_0002

13C-NMR Spectrum of Compound 35

13C-NMR (Acetone- D6) δ: 30.87 (C- 3), 36.21 (C- 2), 118.69 (C- 8), 123.31 (C-5), 123.41 (C- 6), 126.88 (C- 9), 127.37 (C- 4), 128.54 (C-41, C-61), 129.61 (C-31, C-7′), 132.99 (C-51), 134.99 (C-21), 148.03 (C-7), 167.34 (C-I1), 173.94 (C-I ).

Figure imgf000064_0001
Figure imgf000064_0002

13C-NMR Spectrum of Compound 35

Figure imgf000065_0001
Figure imgf000065_0002

COSY-NMR Spectrum of Compound 35

Figure imgf000066_0001
Figure imgf000066_0002

COSY-NMR Spectrum of Compound 35

 

Figure imgf000067_0001

HETCOR-NMR Spectrum of Compound 35

 

Figure imgf000068_0001

 

 

3-[3-(benzoylamino)-4-hydroxylphenyl] propanoic acid 35:

 

To a solution of 32 (222 mg, 1.06 mmol, leq.) dissolved in THF (20 mL) was added the catalyst 10 % palladium-on-charcoal (15 % by mass, 33 mg). The resulting mixture was then placed on a hydrogenator, flushed (5 times) with hydrogen and left to agitate under pressure (36 psi.) overnight (12 hrs) while recharging hydrogen pressure twice (36 psi.) until hydrogen up-take by reaction mixture stopped (pressure did not decrease for 1-2 hrs.). The reaction mixture was vacuum filtered through Celite ‘ rinsing with THF. To the filtered solution containing 33 was directly added BzCl (154 mg, 1.1 mmol, 1 eq.) and left to stir at room temperature for 30 min. Then 10 % HCl (25 mL) was added and stirring continued an additional 5 min. followed by extraction with CIT2Cl2 (2 x 35 mL). The organic fractions were combined, dried (MgSO4), and evaporated off solvent. The resulting mixture was re-crystallized with Hexane/ Acetone to afford an off white solid (250 mg) with an 83 % yield from compound 32. Molecular Formula – C16Hi5NO4. Formula Weight – 285.295 g mole“1.

FT-IR (KBR disk) cm” 1 : 3201 (NH, OH), 1692 (CO2H), 1636 (NHAc).

1H-NMR (Acetone-D6) δ: 2.60 (t, 2H, J = 7.4, H- 3), 2.84 (t, 2H, J = 7.9, H-2), 6.89 (d, IH, J = 8.2, H-8), 7.00 (dd, IH, J = 2.1 , 8.25, H- 9), 7.57 (m, 4H, H-5, H-4′, H-5′, H-61), 8.05 (d, 2H, J = 8.2, H-3′, H-7′), 9.07 (broad s, IH, NH), 9.54 (broad s, IH, OH), 10.58 (broad s, IH, CO2H).

13C-NMR (Acetone- D6) δ: 30.87 (C- 3), 36.21 (C- 2), 118.69 (C- 8), 123.31 (C-5), 123.41 (C- 6), 126.88 (C- 9), 127.37 (C- 4), 128.54 (C-41, C-61), 129.61 (C-31, C-7′), 132.99 (C-51), 134.99 (C-21), 148.03 (C-7), 167.34 (C-I1), 173.94 (C-I ).

/////////////////////////////////////////

 

1H-NMR Spectrum of Compound (+/-V36

Figure imgf000069_0001
Figure imgf000069_0002

13 C-NMR Spectrum of Compound (+/-V36

Figure imgf000070_0001
Figure imgf000070_0002

N-(l-oxaspiro[4.5]deca-6,9-dien-2,8-dion-7-yl)acetamide (+/-)-36: To a solution of 34 (122 mg, .547 mmol, 1 eq.) dissolved in acetone (10 mL, 0 0C) was added PIFA (306 mg, .71 1 mmol, 1.3 eq.) in one portion and stirred for 20-25 minutes (confirmed by tic: [1 : 1] EtOAc/Hexane). The reaction mixture was diluted with ethyl acetate (15 mL), washed with cold water (10 mL), dried organic fraction (MgSO4) and evaporated off solvent to afford a Tan solid. The crude product was purified by re-dissolving with CHCI3, filtering of the solution through Celite ®, evaporating off the solvent and placing it under vacuum overnight to afford an off white solid (120 mg, 98 % yield). Molecular Formula – C1 1Hi iNO4. Formula Weight – 221.209 g mole“1. FT-IR (KBR disk) cm“1: 3333 (NH), 1777 (lactone), 1668 (amide), 1650 (ketone), 1620 (α, β-conjugation to ketone). 1H-NMR (CDCl3) δ: 2.17 (s, 3H, H-2′), 2.44 (m, 2H, H-4), 2.81 (m, 2H, H-3), 6.35 (d, IH, J = 10.0, H-9), 6.94 (dd, IH, J = 3.1, 10.0, H- 10), 7.75 (d, IFI, J = 3.1, H-6), 7.99 (broad s, IH, NH). 13C-NMR (CDCl3) δ: 24.86 (C- 2′), 28.36 (C- 4), 32.91 (C- 3), 79.76 (C-5), 124.30 (C- 6), 127.12 (C- 9), 131.55 (C- 7), 148.37 (C-10), 169.51 (C-I’), 175.46 (C-2), 179.40 (C- 8).

 

////////////////////

1H-NMR Spectrum of Compound 32

Figure imgf000059_0001
Figure imgf000059_0002

(2E)-3-(4-hydroxyl-3-nitrophenyl) acrylic acid 32: To a solution of 4- hydroxyl-3-nitrobenzaldehyde (1.073 g, 6.43 mmol, 1 eq.) dissolved in pyridine (25 mL) was added piperidine (25 drops) and the resulting mixture was stirred (4-5 min.). Malonic acid (1.671 g, 16.1 mmol, 2.5 eq.) was then added in one portion and the resulting mixture was warmed (60-63 0C) and stirred overnight (12-14 hrs, confirmed by tic: EtOAc, mini work up, 10 % HCl and EtOAc). The reaction was cooled and acidified (50 % HCl) until yellow precipitate formed (pH~2). This yellow precipitate was extracted with ethyl acetate (2 x 150 niL). The organic fractions were combined and washed with brine (150 mL), dried (MgSO4), and the solvent was evaporated to afford a yellow solid. Removed excess solvent by vacuum and used without further purification (1.250 g, 93 % yield). Molecular Formula – CgH7NO5. Formula Weight – 209.156 g mole“1. FT-IR (KBR disk) cm“1: 2942 (OH), 1684 (CO2H), 1626 (C=C), 1533,1270 (NO2). 1FI-NMR (Acetone-D6) δ: 2.87 (broad s, IH, OH), 6.58 (d, IH, J= 16.0, H-2), 7.27 (d, IH, J= 8.8, H-8), 7.70 (d, IH, J= 16.4, H-3), 8.08 (d, IH, J= 2.2, 8.5, H-9), 8.40 (d, IFI, J = 2.2, FI-5), 10.67 (broad s, I H, CO2FI). The13C-NMR of this compound agrees with the previously published data.52

 

 

 

Con Dao Island, Vietnam

 

con dau six senses resort image

Con Dao Island, Vietnam

 

This 16-island archipelago is a “pocket of paradise,” says Robert Reid, a travel editor at Lonely Planet.

Getting there: Take a 45-minute flight from Ho Chi Minh City.

What to do: The diving is among the best in Vietnam. Take scuba lessons as a couple or discover the nearby secluded beaches of Bai Dat Doc and Dam Trau.

Where to stay: Six Senses resort offers luxury villas on the East Vietnam Sea. The resort has an in-house spa offering traditional Vietnamese healing practices; it also boasts outdoor treatment rooms and a yoga and meditation pavilion. Inquire for rates.

 

Con Dao travel guide – Wikitravel

wikitravel.org/en/Con_Dao

Con Dao is an island off the southern coast of Vietnam. … The Con Dao Islands separated from the mainland about 15,000 years ago. This has resulted in the …

Understand – ‎Get in – ‎Get around – ‎See

 

 

.

 

 

 

 

 

airport

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

////////////

Share
Follow

Get every new post on this blog delivered to your Inbox.

Join other followers: