4-Pentenoic acid, 5-(3,4-methylenedioxyphenyl)-3-oxo-, ethyl ester

4-Pentenoic acid, 5-(3,4-methylenedioxyphenyl)-3-oxo-, ethyl ester

cas 860547-52-0

MF C14 H14 O5

4-Pentenoic acid, 5-(1,3-benzodioxol-5-yl)-3-oxo-, ethyl ester

Molecular Weight, 262.26

Melting Point (Experimental)

Value: 58-60 °C

Purification of the residue by flash column chromatography (10% ethyl acetate in hexanes) afforded the β-keto ester (12.0 g, 90%) as a pale yellow oil. Compound 3

1H-NMR (400 MHz, CDCl3), δ (ppm):12.00 (s, 0.4 H, enol OH), 7.52 (d, 1H, J = 16.0 Hz, C5 keto ), 7.35 (t, J = 15.6, 1H, C6’ keto), 7.05 (complex, 1.4H, C2’ keto, C2’ enol ), 7.03 (d, J = 12.8, 1H, C5’ keto), 6.97 (d, J = 8.0 Hz, 0.5H, C5’ enol), 6.83-6.78 (m, 1.5H, C6’, C5 and C2 enol), 6.65 (d, J = 16.0 Hz, 1H, C4 keto), 6.27 (d, J = 16 Hz, 0.5H, C4 enol), 6.02 (s, 2H, C7’ keto), 5.98 (s, 1H, C7’ enol), 4.22 (complex, 3H, COOCH2CH3, keto and enol), 3.66 (s, 2H, C2 keto), 1.29 (complex, 4.7H, COOCH2CH3 keto and enol);

13C-NMR (100 MHz, CDCl3), δ (ppm): 191.7, 172.8, 169.4, 167.5, 150.2, 148.8, 148.4, 148.2, 144.4, 136.4, 129.8, 128.4, 125.4, 123.5, 123.2, 119.9, 108.6, 108.5, 106.6, 106.1, 101.7, 101.4, 91.3, 77.3, 77.0, 76.7, 61.4, 60.1, 47.6, 14.2, 14.1.

 

1H NMR PREDICT

 

13C NMR PREDICT

 

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Org. Chem. Front., 2017, Advance Article,
DOI: 10.1039/C7QO00021A

and

1. English, James, Jr.; Journal of the American Chemical Society 1943, V65, P2466-7 
2. (2) Borsche, W.; Berichte der Deutschen Chemischen Gesellschaft [Abteilung] B: Abhandlungen 1933, V66B, P1792-801 

O=C(OCC)CC(=O)/C=C/c1ccc2OCOc2c1

1,3-Diphenylisoquinoline

1,3-Diphenylisoquinoline (3a). Pale-yellow solid (103.5 mg, 92%),

 mp 78-79 oC (lit.24,  73-74.5 oC). 24 J. D. Tovar and T. M. Swager, J. Org. Chem., 1999, 64, 6499

1H NMR (500 MHz, CDCl3) δ 8.25-8.23 (m, 2H), 8.15-8.14 (m, 1H), 8.09 (s, 1H), 7.95-7.93 (m, 1H), 7.84-7.83 (m, 2H), 7.70-7.67 (m, 1H), 7.59-7.50 (m, 6H), 7.44-7.40 (m, 1H);

13C NMR (125 MHz, CDCl3) δ 160.5, 150.3, 140.1, 139.8, 138.0, 130.4, 130.2, 128.8, 128.7, 128.6, 128.4, 127.7, 127.6, 127.2, 127.0, 126.0, 115.8.

Efficient synthesis of isoquinolines in water by a Pd-catalyzed tandem reaction of functionalized alkylnitriles with arylboronic acids

Green Chem., 2017, Advance Article
DOI: 10.1039/C7GC00267J, Paper

Kun Hu, Linjun Qi, Shuling Yu, Tianxing Cheng, Xiaodong Wang, Zhaojun Li, Yuanzhi Xia, Jiuxi Chen, Huayue Wu
Pd-catalyzed tandem reaction of functionalized alkylnitriles with arylboronic acids for the synthesis of diverse isoquinolines in water.

Efficient synthesis of isoquinolines in water by a Pd-catalyzed tandem reaction of functionalized alkylnitriles with arylboronic acids

Kun Hu,^a   Linjun Qi,^a   Shuling Yu,^a   Tianxing Cheng,^a  Xiaodong Wang,^a   Zhaojun Li,^b   Yuanzhi Xia,^a  Jiuxi Chen*^a and   Huayue Wu^a  

 

*Corresponding authors

^aCollege of Chemistry & Materials Engineering, Wenzhou University, Wenzhou 325035, China
E-mail: jiuxichen@wzu.edu.cn

^bInstitute of Agricultural Resources and Regional Planning, Chinese Academy of Agricultural Sciences, Key Laboratory of Plant Nutrition and Fertilizer, Ministry of Agriculture, Beijing, China

Green Chem., 2017, Advance Article

DOI: 10.1039/C7GC00267J, 

A palladium-catalyzed tandem reaction of 2-(cyanomethyl)benzonitriles or 2-(2-carbonylphenyl)acetonitriles with arylboronic acids in water has been developed for the first time. This reaction features good functional group tolerance and provides a new strategy for the synthesis of diverse isoquinolines under mild conditions. The use of water as the reaction medium makes the synthesis process environmentally benign. Preliminary mechanistic experiments indicate that the major reaction pathway involves carbopalladation of the C(sp³)–cyano group and subsequent intramolecular cyclization findings that were further supported by density functional theory (DFT) calculations.

1,3-Diphenylisoquinoline (3a). Pale-yellow solid (103.5 mg, 92%),

 mp 78-79 oC (lit.24,  73-74.5 oC). 24 J. D. Tovar and T. M. Swager, J. Org. Chem., 1999, 64, 6499

1H NMR (500 MHz, CDCl3) δ 8.25-8.23 (m, 2H), 8.15-8.14 (m, 1H), 8.09 (s, 1H), 7.95-7.93 (m, 1H), 7.84-7.83 (m, 2H), 7.70-7.67 (m, 1H), 7.59-7.50 (m, 6H), 7.44-7.40 (m, 1H); 

13C NMR (125 MHz, CDCl3) δ 160.5, 150.3, 140.1, 139.8, 138.0, 130.4, 130.2, 128.8, 128.7, 128.6, 128.4, 127.7, 127.6, 127.2, 127.0, 126.0, 115.8. 

//////// isoquinoline, pd-catalyzed, arylboronic acids

(E)-2-(fluoro(phenyl)methylene)cyclopentan-1-one

Silver-initiated radical ring expansion/fluorination of ethynyl cyclobutanols: efficient synthesis of monofluoroethenyl cyclopentanones

Green Chem., 2016, Advance Article
DOI: 10.1039/C6GC02656G, Communication

Qingshan Tian, Bin Chen, Guozhu Zhang
A stereoselective synthesis of [small beta]-halogenated 2-methylenecyclopentanones via silver-catalyzed formal ring expansion using water as the cosolvent is described.

Silver-initiated radical ring expansion/fluorination of ethynyl cyclobutanols: efficient synthesis of monofluoroethenyl cyclopentanones

Qingshan Tian,^a   Bin Chen^a and   Guozhu Zhang*^a  

*

Corresponding authors

^a

State Key Laboratory of Organometallic Chemistry Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 345 Lingling Road, Shanghai 200032, P. R. China
E-mail: guozhuzhang@sioc.ac.cn

Green Chem., 2016, Advance Article

DOI: 10.1039/C6GC02656G

A stereoselective synthesis of β-halogenated 2-methylenecyclopentanones via silver-catalyzed formal ring expansion using water as the cosolvent is described. A variety of 2-methylenecyclopentanones with fluoro, chloro and bromo functionalities are efficiently prepared from 1-alkynyl cyclobutanols. This method offers facile access to halogenated complex molecules which are not only useful chemicals but also valuable building blocks for further derivatizations.

1-(m-tolylethynyl)cyclobutan-1-ol (1b) Yield: 89%; Yellow oil;

1H NMR (400 MHz, CDCl3)

δ 7.25 (s, 1H), 7.23 (d, J = 8.1 Hz, 1H), 7.18 (t, J = 7.5 Hz, 1H), 7.10 (d, J = 7.5 Hz, 1H), 2.51 (dt, J = 15.8, 6.3 Hz, 2H), 2.34 (t, J = 9.3 Hz, 2H), 2.30 (s, 3H), 1.85 (m, 2H);

13C NMR (100 MHz, CDCl3)

δ 137.94, 132.27, 129.19, 128.72, 128.17, 122.49, 92.16, 83.58, 68.31, 38.64, 21.20, 12.98; HRMS (EI+ , 70 eV): C13H14O [M]+ : calcd. 186.1045, found 186.1047

(E)-2-(fluoro(phenyl)methylene)cyclopentan-1-one (2a) Yield: 85%; Colorless oil;

1H NMR (400 MHz, CDCl3) δ 7.79 (dd, J = 8.0, 1.5 Hz, 2H), 7.46-7.40 (m, 3H), 2.94 (td, J = 7.3, 3.3 Hz, 2H), 2.43 (td, J = 7.9, 1.2 Hz, 2H),1.99 (m, 2H);

13C NMR (100 MHz, CDCl3) δ 204.7 (d, J = 14.4 Hz), 162.4 (d, J = 270.7 Hz), 131.1, 130.0, 129.7, 128.7 (d, J = 7.0 Hz), 127.8, 117.3 (d, J = 19.4 Hz), 40.7 (d, J = 4.3 Hz), 27.6 (d, J = 3.9 Hz), 19.4;

19F (376 MHz, CDCl3) δ -76.9;

HRMS (EI+ , 70 eV): C12H11FO [M]+ : calcd. 190.0794, found 190.0795.

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1,2-bis((5-bromopyridine-2-yl)diazene oxide

 

1,2-bis((5-bromopyridine-2-yl)diazene oxide

1H NMR (DMSO): δ in ppm (integral, multiplicity, Hz) 8.83 (1H, dd, 0.56, 2.38) 8.82 (1H, dd, 0.64, 2.49) 8.48 (1H, dd, 2.40, 8.65) 8.28 (1H, dd, 0.60, 8.64) 8.02 (1H, dd, 0.67,8.69)

13C NMR (DMSO): δ in ppm (type of carbon) 150.33 (C-H), 149.48 (C-H), 142.74 (C-H), 140.86 (C-H), 119.60 (C-H), 119.46 (C-H)

LC/MS data (ESI) 358.8981 ([M+H]+ ), 380.8789 ([M+Na]+ )

Org. Process Res. Dev., Article ASAP

DOI: 10.1021/acs.oprd.6b00433

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(S,S,S)-2-aza-bicyclo-[3.3.0]- octane-3-carboxylic acid benzyl ester, Ramipril intermediate

93779-31-8 cas

Cyclopenta[b]pyrrole-2-carboxylicacid, octahydro-, phenylmethyl ester, (2S,3aS,6aS)-

Formula:	C15H20ClNO2
Molecular Weight:	281.78

cas 93779-29-4

(S,S,S)-2-aza-bicyclo-[3.3.0]- octane-3-carboxylic acid benzyl ester

(S,S,S)-2-aza-bicyclo-[3.3.0]- octane-3-carboxylic acid benzyl ester, white solid. Yield 33.7 g (95%); mp 178–180 8C (lit.[6c] mp 180 8C); [a]D 20 ¼ 240.0 (c ¼ 1, H2O) [lit.[6c] [a]D 30 ¼ 238.4 (c ¼ 1, H2O)];

 1H NMR (400 MHz, CDCl3) d 1.36–1.42 (m, 1H), 1.58–1.75 (m, 2H), 1.82–2.01 (m, 3H), 2.32–2.37 (m, 1H), 2.58 (dt, J ¼ 13.2, 8.4 Hz, 1H), 2.83–2.88 (m, 1H), 4.31 (td, J ¼ 8.0, 3.6 Hz, 1H), 4.43 (t, J ¼ 8.4 Hz, 1H), 5.20 (AB q,J ¼ 12.0 Hz, 2H), 7.33–7.37 (m, 5H); 13C NMR (50 MHz, DMSO) d 24.07, 29.60, 31.02, 33.45, 41.37, 60.11, 63.81, 66.99, 128.11, 128.28, 128.43, 135.14, 167.32; FT IR (KBr disc) 1758 cm21; MS: m/e 246 (Mþ).

(c) Teetz, V.;
Geiger, R.; Gaul, H. Synthesis of unnatural amino acids: (S,S,S)-2-azabicyclo-
[3.3.0]-octane-3-carboxylic acid. Tetrahedron Lett. 1984, 25, 4479.

2-Methoxy-4-propylphenol

 

2-Methoxy-4-propylphenol

2-Methoxy-4-propylphenol
1H NMR (400 Mhz, CDCl3) δ (ppm): 6.83 (1H,d, J = 7.8 Hz), 6.68 (2H, d, J = 7.4 Hz), 5.47 (1H, s), 3.79 (3H, s), 2.52 (2H, t, J =7.6 Hz), 1.61 (2H, sext, J = 7.5 Hz) 0.94 (3H, t, J = 7.3 Hz).

13C NMR (100 MHz, CDCl3) δ (ppm) 146.4, 143.6,134.7, 121.0, 114.2, 111.1, 55.9, 37.8, 24.9, 13.8.

HRMS (ESI-TOF) m/z: [M + H]+ calculated for C10H15O2:167.1067; found: 167.1064.

DOI: 10.1021/acs.oprd.6b00441

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A Brønsted acid catalysed enantioselective Biginelli reaction

A Bronsted acid catalysed enantioselective Biginelli reaction

Green Chem., 2017, Advance Article
DOI: 10.1039/C6GC03274E, Paper

Margherita Barbero, Silvano Cadamuro, Stefano Dughera
A chiral derivative of 1,2-benzenedisulfonimide, namely (-)-4,5-dimethyl-3,6-bis(o-tolyl)-1,2-benzenedisulfonimide is herein proven to be an efficient chiral catalyst in a one pot three-component Biginelli reaction.

A Brønsted acid catalysed enantioselective Biginelli reaction

Margherita Barbero,a   Silvano Cadamuroa and  Stefano Dughera*a  

*Corresponding authors

aDipartimento di Chimica, Università di Torino, C.so Massimo d'Azeglio 48, 10125 Torino, Italy
E-mail: stefano.dughera@unito.it

Green Chem., 2017, Advance Article

DOI: 10.1039/C6GC03274E

A chiral derivative of 1,2-benzenedisulfonimide, namely (−)-4,5-dimethyl-3,6-bis(o-tolyl)-1,2-benzenedisulfonimide is herein proven to be an efficient chiral catalyst in a one pot three-component Biginelli reaction. In fact the yields of the target dihydropyrimidines were very high (25 examples; average 91%) and enantiomeric excesses were always excellent (14 examples; average 97%). Ultimately, we herein propose a procedure that displays a number of benefits and advantages including the total absence of solvents, mild reaction conditions, relatively short reaction times and stoichiometric reagent ratios. Target dihydropyrimidines are obtained in adequate purity, making further chromatographic purification unnecessary. Moreover, the chiral catalyst was easily recovered from the reaction mixture and reused, without the loss of catalytic activity.

(R)-(-)-Ethyl 6-methyl-4-phenyl-2-thioxo-3,4-dihydropyrimidine-5-carboxylate (5a): pale grey solid (135 mg, 98% yield); mp 201–202 °C ( from EtOH; lit17 200–202 °C). 96.4% Ee (GC connected to a J&W Scientific Cyclosil-B column; stationary phase: 30% heptakis (2,3-di-Omethyl-6-O-t-butyldimethylsilyl)-β-cyclodextrin in DB-1701), tR= 12.11 min (major), tR= 12.54 min (minor); [a]D -65.4 (c 0.1 in MeOH).

1H NMR (200 MHz, DMSO-d6): δ = 10.24 (br s, 1H), 9.55 (br s, 1H), 7.31–7.12 (m, 5H), 5.09 (d, J = 3.9 Hz, 1H), 3.92 (q, J = 7.0 Hz, 2H), 2.21 (s, 3H), 1.01 (t, J = 7.0 Hz, 3H);

13C NMR (50 MHz, DMSO-d6): δ = 174.9, 165.8, 145.7, 129.3, 128.3, 127.0, 101.3, 60.2, 54.7, 17.8, 14.7.

MS (m/z, EI): 276 [M+ ] (45), 247 (40), 199 (100). IR (neat) ν (cm−1): 3311 (NH), 3112 (NH), 1665 (CO), 1195 (CS).

USES

////////////Bronsted acid,  catalysed, enantioselective, Biginelli reaction