Benzyl (5-methylpyrazin-2-yl)carbamate

2-(Cbz-Amino)-5-methylpyrazine

Molecular Formula:	C13H13N3O2
Molecular Weight:	243.266 g/mol

 

 

Benzyl (5-methylpyrazin-2-yl)carbamate

CAS 1033418-57-3

Mp 191.4 °C.

IR 1719, 1567, 1353, 1226, 1054, 759, 744, 706 cm–1.

1H NMR (DMSO-d6, 500 MHz) 10.45 (br, 1H), 8.93 (s, 1H), 8.20 (s, 1H), 7.42–7.32 (m, 5H), 5.18 (s, 2H), 2.41 (s, 3H).

13C NMR (DMSO-d6, 125.7 MHz) 153.6, 147.7, 146.7, 141.7, 136.5, 134.3, 128.7 (2C), 128.4, 128.2 (2C), 66.5, 20.4.

HRMS elemental calculated for C13H14N3O2 (MH+): 244.1086; found: 244.1080.

NMR PREDICT

1H NMR

13 C NMR PREDICT

Use of a Curtius Rearrangement as Part of the Multikilogram Manufacture of a Pyrazine Building Block

Alan Steven*†  and Phillip Hopes‡

† Pharmaceutical Technology & Development, AstraZeneca, Charter Way, Macclesfield, SK10 2NA, United Kingdom

‡ Cyton Biosciences Ltd., 68 Macrae Road, Bristol, BS20 0DD, United Kingdom

Org. Process Res. Dev., Article ASAP

DOI: 10.1021/acs.oprd.7b00340

 

*E-mail: Alan.Steven@astrazeneca.com.

http://pubs.acs.org/doi/10.1021/acs.oprd.7b00340

 

 

MORE...............

 

A modular flow reactor for performing Curtius rearrangements as a continuous flow process

Marcus Baumann,a  Ian R. Baxendale,a  Steven V. Ley,*a  Nikzad Nikbin,a  Christopher D. Smitha  and Jason P. Tierneyb 

*Corresponding authors

aInnovative Technology Centre, Department of Chemistry, University of Cambridge, Lensfield Road, Cambridge, UK
E-mail: svl1000@cam.ac.uk
Fax: +44 1223 336442
Tel: +44 1223 336398

bNeurology Lead Discovery Chemistry, Neurology CEDD, GlaxoSmithKline R and D, New Frontiers Science Park (North), Third Avenue, Harlow, UK

Abstract

The use of a mesofluidic flow reactor is described for performing Curtius rearrangement reactions of carboxylic acids in the presence of diphenylphosphoryl azide and trapping of the intermediate isocyanates with various nucleophiles.

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O=C(OCc1ccccc1)Nc2cnc(C)cn2

Ruthenium-Catalyzed Tandem C–H Fluoromethylation/Cyclization of N-Alkylhydrazones with CBr3F: Access to 4-Fluoropyrazoles

4-Fluoropyrazoles are accessible in a single step from readily available aldehyde-derived N-alkylhydrazones through double C–H fluoroalkylation with tribromofluoromethane (CBr3F). RuCl2(PPh3)3 has been proven to be the most efficient catalyst for this transformation when compared to a range of other Cu-, Pd-, or Fe-based catalyst systems.

Alexis Prieto

Alexis Prieto, Didier Bouyssi*, and Nuno Monteiro* 

Univ Lyon, Université Claude Bernard Lyon 1, Institut de Chimie et Biochimie Moléculaires et Supramoléculaires (ICBMS, CNRS UMR 5246), F-69622 Villeurbanne, France

J. Org. Chem., 2017, 82 (6), pp 3311–3316

DOI: 10.1021/acs.joc.7b00085

*E-mail: didier.bouyssi@univ-lyon1.fr., *E-mail: nuno.monteiro@univ-lyon1.fr.

Ruthenium-Catalyzed Tandem C–H Fluoromethylation/Cyclization of N-Alkylhydrazones with CF3BR: Access to 4-Fluoropyrazoles

http://pubs.acs.org/doi/10.1021/acs.joc.7b00085

---

The importance of fluorine-containing pyrazoles to the pharmaceutical and agrochemical industries has been steadily increasing in recent years. As a consequence, the development of methods suitable for the incorporation of fluorine or fluoroalkyl groups into the pyrazole ring continues to be the subject of intense research.

Predicated on their previous copper-catalyzed synthesis of 4-substituted pyrazoles, Bouyssi, Monteiro and their co-worker from the Institut de Chemie et Biochemie Moléculaires et Supramoléculaires reported a ruthenium-catalyzed synthesis of substituted-4-fluoropyrazoles ( J. Org. Chem. 2017, 82, 3311). The requisite starting materials, aldehyde derived N,N-dialkylhydrazones, were readily synthesized. Tribromofluoromethane served as the source of fluorine.

The commercially available and inexpensive ruthenium complex, RuCl2(PPh3)3, was discovered to be a very effective catalyst for this transformation. Diglyme was the preferred solvent for the reaction. The reaction displayed good tolerance for a variety of functional groups, including cyano, ester, formyl, and halide.

In general, higher yields were obtained with electron-withdrawing substituents. This novel methodology affords substituted-4-fluoropyrazoles in good yields in one step from readily available starting materials.

                                                 2K

3-(Benzo[d][1,3]dioxol-5-yl)-4-fluoro-1-methyl-1H-pyrazole (2k)

Chromatography using ethyl acetate/cyclohexane (gradient elution 30:70 to 50:50) gave the title compound as a pale yellow solid (79 mg, 60%).

Mp = 82–85 °C.

1H NMR (400 MHz, CDCl3) δ 7.35–7.31 (m, 2H), 7.27 (d, J = 4.8 Hz, 1H), 6.85 (d, J = 8.5 Hz, 1H), 5.97 (s, 2H), 3.83 (s, 3H).

13C NMR (101 MHz, CDCl3) δ 148.0, 147.2, 146.8 (d, J = 248.0 Hz), 136.7 (d, J = 6.2 Hz), 125.3 (d, J = 4.2 Hz), 119.8 (d, J = 4.7 Hz), 117.5 (d, J = 28.6 Hz), 108.6, 106.6 (d, J = 3.7 Hz), 101.1, 40.0 (s).

19F NMR (282 MHz, CDCl3) δ −178.2 (s). HRMS (ESI): Calcd for C11H10FN2O2 [M + H+]: 221.0721, found 221.0728.

Alexis prieto

Chercheur postdoctoral chez Melchiorre group, ICIQ

Melchiorre group, ICIQ

Didier Bouyssi

Univ Lyon, Université Claude Bernard Lyon 1, Institut de Chimie et Biochimie Moléculaires et Supramoléculaires (ICBMS, CNRS UMR 5246), F-69622 Villeurbanne, France

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“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

2,4-dimorpholinocyclopent-2-enone

1465003-25-1 cas

2,4-dimorpholinocyclopent-2-enone (1b):

1H NMR (300 MHz, CDCl3) 6.24 (d, J = 2.9 Hz, 1H, COC=CH), 3.78 (t, J = 4.7 Hz, 4H, morpholine), 3.73 (t, J = 4.7 Hz, 4H, morpholine), 3.73-3.72 (m, 1H, COCH2CHN), 3.15-3.14 (m, 4H, morpholine), 2.54-2.52 (m, 4H, morpholine), 2.49-2.48 (m, 1H, COCH2), 2.46-2.45 (m, 1H, COCH2);

13C NMR (75 MHz, CDCl3) 38.1, 48.1, 50.0, 60.3, 66.6, 67.1, 129.5, 151.7, 202.0.

Water excellent solvent for the synthesis of bifunctionalized cyclopentenones from furfural

M. Nardi,*ab  P. Costanzo,c  A. De Nino,a  M. L. Di Gioia,d  F. Olivito,c  G. Sindonaa  and  A. Procopioc 

*Corresponding authors

aDipartimento di Chimica, Università della Calabria, Cubo 12C, 87036-Arcavacata di Rende, Italy
E-mail: monica.nardi@unical.it
Fax: +39 0984493307
Tel: +39 0984 492850

bDipartimento di Agraria, Università Telematica San Raffaele, 247, Roma Via di Val Cannuta, Italy

cDipartimento di Scienze della Salute, Università Magna Graecia, Viale Europa, 88100-Germaneto, Italy

dDipartimento di Farmacia e Scienze della Salute e della Nutrizione, Edificio Polifunzionale, Università della Calabria, 87030 Arcavacata di Rende, Italy

Abstract

Chiral cyclopentenones are important precursors in the asymmetric synthesis of target molecules. In particular, C-2 amino cyclopentenones could be utilised as intermediates towards antitumor natural products. On the basis of our previous experience, we report an environmentally friendly protocol for the synthesis of bifunctionalized cyclopentenones in water from furfural. The use of water and MW gives high regioselectivity and good to excellent yields. The reaction can be realized in short times with various nucleophiles.

Monica Nardi

PostDoc

Università della Calabria , Rende · Dipartimento di Chimica e Tecnologie Chimiche - CTC

Università della Calabria

Department

• Dipartimento di Chimica e Tecnologie Chimiche - CTC

• Research experience

  • Oct 2014–present

    Visiting Lectur

    The School of Pharmacy · School of Pharmacy · Prof Steve Brocchini
    United Kingdom · London
  • Jan 2014–present

    PostDoc Position

    Università della Calabria · Department of Pharmacy, Health and Nutritional Sciences
    Italy · Rende
  • Mar 2001–Sep 2014

    PostDoc

    Università della Calabria · Department of Management
    Italy · Rende
  • Mar 2001–Dec 2013

    PostDoc Position

    Università della Calabria · Dipartimento di Chimica e Tecnologie Chimiche - CTC · Prof Giovanni Sindona
    Italy · Rende

Dipartimento di Chimica, Università della Calabria

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1 Estevão, Mónica S.; Afonso, Carlos A.M.; Tetrahedron Letters; vol. 58; nb. 4; (2017); p. 302 - 304

2  Green Chemistry; vol. 19; nb. 1; (2017); p. 164 - 168



“ORG SPECT 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

1,1'-(4'-(tert-butoxy)-4-(dimethylamino)-[1,1'-biphenyl]-2,6-diyl)diethanone

1,1'-(4'-(tert-butoxy)-4-(dimethylamino)-[1,1'-biphenyl]-2,6-diyl)diethanone

NMR IS EASY

MOM CAN TEACH

13C NMR PREDICT

CC(C)(C)Oc1ccc(cc1)c2c(cc(cc2C(C)=O)N(C)C)C(C)=O

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“ORG SPECT 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

Zhong-Xia WANG

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.

 

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

 

*E-mail: zxwang@ustc.edu.cn.

Abstract

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 S^2– 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

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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