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Showing posts with label nmr. Show all posts
Showing posts with label nmr. Show all posts

Friday, 20 October 2017

Ethyl(1R,2S,3S,4S)-2-(furan-2-yl)-3-nitro-6-oxobicyclo[2.2.2]octane-1-carboxylate



Ethyl(1R,2S,3S,4S)-2-(furan-2-yl)-3-nitro-6-oxobicyclo[2.2.2]octane-1-carboxylate


Compound 7 Ethyl(1R,2S,3S,4S)-2-(furan-2-yl)-3-nitro-6-oxobicyclo[2.2.2]octane-1-carboxylate To a solution of CAT 10 (128 mg, 0.37 mmol) and the nitroolefin 9 (3.1 g, 22.3 mmol) in 10 mL anhydrous CH2Cl2 at room temperature was added enone 8 (1.8 g, 10.7 mmol). The resulting mixture was stirred at the same temperature until enone 8 is consumed as indicated by TLC. Then DBU (0.34 mL, 3.20 mmol) was added and the mixture was allowed to stir at ambient temperature until completion as indicated by TLC. The solution was concentrated in vacuo and purified by flash chromatography on silica gel (Hexane / EtOAc = 20 / 1) to give 7 (2 g, 61% yield) as a yellow solid. [α]D 23 28.0 (c = 1.0, CHCl3).

1H NMR (400 MHz, CDCl3): δ 7.29 (d, J = 0.8 Hz, 1H), 6.27 (dd, J = 2.0 Hz, J = 3.2 Hz, 1H), 6.14 (d, J = 4.0 Hz, 1H), 4.93 (m, 1H), 4.57 (d, J = 4.4 Hz, 1H), 4.11 (m, 2H), 3.04-3.02 (m, 1H), 2.80-2.75 (m, 1H), 2.60- 2.54 (m, 1H), 2.33-2.29 (m, 1H), 1.88-1.72 (m, 2H), 1.33-1.23 (m, 1H), 1.21 (t, J = 7.2 Hz, 3H).

13C NMR (100 MHz, CDCl3): δ 204.1, 168.7, 151.8, 142.5, 110.5, 108.1, 88.3, 61.3, 56.3, 42.0, 40.8, 33.7, 26.9, 19.2, 13.8.

IR (thin film): 3435, 3141, 3120, 2996, 2959, 1715, 1653, 1621, 1557, 1505, 1473, 1443, 1408, 1371, 1336, 1301, 1336, 1301, 1270, 1236, 1142, 1120, 1083, 1062, 1074, 1045, 1045, 1011, 996, 960, 930, 892, 884, 867, 803, 753, 628, 600, 508, 436 cm-1 .

LRMS (ESI): 308.0 (M+H)+ , 330.0 (M+Na)+ .

 HRMS (ESI): calcd for C15H18O6N (M+H) + : 308.1129. Found: 308.1130.

 Melting point: 117-118 oC.


Concise asymmetric total synthesis of (−)-patchouli alcohol

 Author affiliations

Abstract

The asymmetric total synthesis of (−)-patchouli alcohol was accomplished in a concise manner. Key reactions include a highly diastereo- and enantioselective formal organocatalytic [4 + 2] cycloaddition reaction, a radical denitration reaction, and an oxidative carboxylation reaction. The formal synthesis of norpatchoulenol was achieved as well.
Graphical abstract: Concise asymmetric total synthesis of (−)-patchouli alcohol

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Thursday, 19 October 2017

2-Methyl-3-tosyl-1,2,3,4-tetrahydroquinazoline

Image result for NMR IN COLOUR



Two-dimensional proton–proton NMR correlation spectrum of 2-methyl-3-tosyl-1,2,3,4-tetrahydroquinazoline in acetone-d6. A colour code was used to highlight the observed H–H couplings.



image file: c6ra20886j-s2.tif


Scheme 2 Pd-mediated hydrolysis of triethylamine in the presence of 2-tosylaminomethylaniline (HATs) to yield 2-methyl-3-tosyl-1,2,3,4-tetrahydroquinazoline and di(acetato)bis(diethylamine)palladium(II).

2-Methyl-3-tosyl-1,2,3,4-tetrahydroquinazoline

Yield = 12.3 mg (41%). 1H NMR (400 MHz, dmso-d6): δ/ppm 7.56 (d, J = 8.2 Hz, 2H, 2 × H-2′), 7.16 (d, J = 8.1 Hz, 2H, 2 × H-3′), 6.83 (m, 2H, H-5 + H-7), 6.46 (t, J = 7.1, 1H, H-6), 6.25 (d, J = 8.1 Hz, 1H, H-8), 6.09 (d, J = 3.4 Hz, 1H, NH), 5.22 (m, 1H, H-2), 4.54 (d, J = 17.2 Hz, 1H, CHH-4) and 4.36 (d, J = 17.2 Hz, 1H, CHH-4), 2.25 (s, 3H, CH3-4′) and 1.22 (d, 3H, J = 6.3 Hz, CH3-2). 1H NMR (250 MHz, CDCl3): δ/ppm 7.59 (d, J = 8.3 Hz, 2H, 2 × H-2′), 7.06 (d, J = 8.3 Hz, 2H, 2 × H-3′), 6.90 (t, 1H, H-7), 6.86 (d, 1H, H-5), 6.67 (dt, J = 7.5 and 1.1 Hz, 1H, H-6), 6.29 (d, J = 8.1 Hz, 1H, H-8), 5.36 (dq, J = 6.4 and 1.0 Hz, 1H, H-2), 4.70 (d, J = 17.4 Hz, 1H, CH2-4), 4.47 (d, J = 17.4 Hz, 1H, CH2-4), 2.29 (s, 3H, CH3) and 1.40 (d, J = 6.4 Hz, 3H, CH3). 13C NMR (62.5 MHz, CDCl3): δ/ppm 143.2 (C4′), 139.7 (C8a), 136.2 (C1′), 129.0 (2 × C3′), 127.6 (C5), 127.3 (2 × C2′), 126.4 (C7), 118.8 (C6), 116.9 (C4a), 116.4 (C8), 61.4 (CH), 41.8 (CH2), 21.5 (CH3) and 21.4 (CH3). IR (KBr, cm−1): 3387(s) ν(NH) cm−1, 1326(s) νas(SO2), 1158(vs) νs(SO2). MS (ESI) m/z = 325 (MNa+). HRMS calcd for C16H18N2NaO2S (MNa+): 325.0981; found, 325.0967. Elemental analysis (found): C 63.5, H 5.8, N 9.1; S, 10.5%. Calc. for C16H18N2O2S: C, 63.6; H, 6.0; N, 9.3; S, 10.6%.




http://pubs.rsc.org/en/content/articlehtml/2016/RA/C6RA20886J


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Thursday, 28 September 2017

Development of a General Protocol To Prepare 2H-1,3-Benzoxazine Derivatives

Figure
2H-1,3-Benzoxazine natural products and related bioactive molecules.

4-(2-Bromo-5-chlorobenzyl)-7-chloro-2-phenyl-2H-benzo[e][1,3]oxazine 2 as a light-yellow solid (82% yield).
1H NMR (500 MHz, CDCl3): δ (ppm) 7.55–7.52 (m, 3H), 7.42–7.34 (m, 3H), 7.30 (d, 1H, J = 3.5 Hz,) 7.29 (s, 1H), 7.12 (dd, 1H, J = 8.5 Hz, 2.5 Hz), 6.95–6.91 (m, 2H), 6.57 (1H, s), 4.16 (ABq, 2H, ΔδAB = 0.05, JAB = 16.5 Hz).
13C NMR (125 MHz, CDCl3): δ (ppm) 161.5, 155.8, 139.2, 138.9, 138.1, 133.8, 133.5, 130.6, 128.8, 128.7, 128.5, 127.0, 126.3, 122.6, 121.9, 117.3, 116.2, 88.9, 40.8.
HRMS TOF MS (m/z): [M + H]+ calcd for [C21H14BrCl2NO H] 445.9709; found 445.9713.
FTIR(neat): 3060, 1633, 1596, 1454, 1364, 1344 cm–1.
Spectroscopic data for 2 were identical to those reported in the literature.(4)
LiH.BelykK. M.YinJ.ChenQ.HydeA.JiY.OliverS.TudgeM.CampeauL.-C.CamposK. R. J. Am. Chem. Soc. 2015137,13728– 13731 DOI: 10.1021/jacs.5b05934

Development of a General Protocol To Prepare 2H-1,3-Benzoxazine Derivatives

 Department of Process Research and Development, MSD R&D (China) Co., Ltd., Building 21 Rongda Road, Wangjing R&D Base, Zhongguancun Electronic Zone West Zone, Beijing 100012, China
 Department of Process Research and Development, Merck Sharp & Dohme, Hertford Road, Hoddesdon, Hertfordshire EN11 9BU, United Kingdom
§ Department of Synthetic Chemistry, Pharmaron Beijing Co., Ltd., 6 Taihe Road BDA, Beijing, 100176, China
 Department of Process Research and Development, Merck Research Laboratories, P.O. Box 2000, Rahway, New Jersey 07065, United States
Org. Process Res. Dev., Article ASAP
DOI: 10.1021/acs.oprd.7b00209
Publication Date (Web): August 23, 2017
Copyright © 2017 American Chemical Society
*E-mail: ji_qi@merck.com.
ACS Editors’ Choice – This is an open access article published under an ACS AuthorChoice License, which permits copying and redistribution of the article or any adaptations for non-commercial purposes.

Abstract

Abstract Image
A practical synthesis and detailed development process of 2H-1,3-benzoxazine derivatives catalyzed by aldimine and trifluoromethanesulfonic acid is described. A broad range of substrates with diverse steric and electronic properties were explored. Aliphatic/aromatic/heteroaromatic substrates all proceed well under conditions which have been optimized into a robust, scalable process.

Wednesday, 20 September 2017

Catalyst-free multi-component cascade C–H-functionalization in water using molecular oxygen: an approach to 1,3-oxazines


 

Catalyst-free multi-component cascade C-H-functionalization in water using molecular oxygen: an approach to 1,3-oxazines
Green Chem., 2017, 19,4036-4042
DOI: 10.1039/C7GC01494E, Communication
Mohit L. Deb, Choitanya D. Pegu, Paran J. Borpatra, Prakash J. Saikia, Pranjal K. Baruah
Synthesis of 1,3-oxazines via catalyst free C-H functionalization using molecular oxygen in water.

Catalyst-free multi-component cascade C–H-functionalization in water using molecular oxygen: an approach to 1,3-oxazines


 Author affiliations

Abstract

Herein, catalyst-free 3-component reactions of naphthols, aldehydes, and tetrahydroisoquinolines to synthesize 1,3-oxazines is reported. The reaction is performed in H2O in the presence of O2 as the sole oxidant at 100 °C, which proceeds through the formation of 1-aminoalkyl-2-naphthols followed by selective α-C–H functionalization of tert-amine.
15-phenyl-7a,12,13,15-tetrahydronaphtho[1',2':5,6][1,3]oxazino[2,3- a]isoquinoline (4a):1
White solid; Yield 61 %, 221 mg;
1H NMR (500 MHz, CDCl3): δ 7.79-7.77 (m, 1H), 7.74 (d, J = 8.9 Hz, 1H), 7.43-7.41 (m, 1H), 7.33-7.28 (m, 8H), 7.24-7.19 (m, 3H), 7.11 (d, J = 8.9 Hz, 1H), 5.65 (s, 1H), 5.44 (s, 1H), 3.40-3.26 (m, 2H), 3.12-3.09 (m, 1H), 2.90- 2.86 (m, 1H);
13C NMR (125 MHz, CDCl3): δ 151.9, 142.3, 135.0, 133.0, 132.4, 129.3, 129.1, 128.9, 128.8 (2C), 128.7, 128.6, 128.2, 127.4, 126.5, 126.2, 123.1, 122.7, 118.9, 110.9, 82.2, 62.6, 45.4, 29.4;
HRMS (ESI) exact mass calculated for C26H21NO [M+H]+ : 364.1701; found: 364.1705.
The representative procedure for the synthesis of 4a is as follows: 2-naphthol (1a, 144 mg, 1 mmol), benzaldehyde (2a, 106 mg, 1 mmol), tetrahydroisoquinoline (3, 133 mg, 1 mmol) and water (1.5 mL) were added in a round-bottom flask equipped with a magnetic stirring bar and a reflux condenser. The whole apparatus was efficiently flushed with oxygen gas and then connected to a balloon filled with oxygen. After vigorous stirring at 100 oC for 12 h, water was removed under vacuum and purified the reaction mixture by column chromatography (100-200 mesh silica gel, hexane-ethyl acetate) to obtain the product 4a as white solid. The other 1,3-oxazines were synthesized and purified by following the procedure described above
str4
STR7str6
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Sunday, 17 September 2017

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.




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

 Author affiliations
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Ex Situ Generation of Sulfuryl Fluoride for the Synthesis of Aryl Fluorosulfates

Abstract Image
A convenient transformation of phenols into the corresponding aryl fluorosulfates is presented: the first protocol to completely circumvent direct handling of gaseous sulfuryl fluoride (SO2F2). The proposed method employs 1,1′-sulfonyldiimidazole as a precursor to generate near-stoichiometric amounts of SO2F2 gas using a two-chamber reactor. With NMR studies, it was shown that this ex situ gas evolution is extremely rapid, and a variety of phenols and hydroxylated heteroarenes were fluorosulfated in good to excellent yields.

Ex Situ Generation of Sulfuryl Fluoride for the Synthesis of Aryl Fluorosulfates

Molecular Design and Synthesis, Department of Chemistry, KU Leuven, Celestijnenlaan 200F, Box 2404, 3001 Leuven, Belgium
Org. Lett., Article ASAP
DOI: 10.1021/acs.orglett.7b02522

http://pubs.acs.org/doi/abs/10.1021/acs.orglett.7b02522?utm_content=bufferd3ad9&utm_medium=social&utm_source=twitter.com&utm_campaign=buffer

4-fluoro-[1,1'-biphenyl]-4-yl sulfurofluoridate (compound 1) 
General procedure A was followed using 192 mg of 4-fluoro-4’-hydroxybiphenyl (98 wt%, 1.0 mmol, 1.0 eq.). The crude reaction mixture was purified by solid-phase flash column chromatography on silicagel (heptane, 100%). The title compound was obtained as a white solid (258 mg, 96%). Rf = 0.39 (heptane/ethyl acetate, 9/1). Melting point = 47 – 49 °C.
1 H NMR (400 MHz, CDCl3): 7.62 (d, J = 8.5 Hz, 1H), 7.52 (dd, J = 8.1, 5.5 Hz, 1H), 7.41 (d, J = 8.5 Hz, 1H), 7.16 (t, J = 8.5 Hz, 1H). 
13C NMR (101 MHz, CDCl3): δ 163.05 (d, J = 247.9 Hz), 149.51, 141.17, 135.55 (d, J = 3.3 Hz), 129.06, 128.98, 121.42, 116.13 (d, J = 21.6 Hz).
19F NMR (376 MHz, CDCl3): δ 37.18, -114.68 (m).
 IR (neat) cm-1 : 1437, 1232, 921, 815. 
CHN: calculated for C12H8F2O3S: C 53.33%, H 2.98%, N 0.00%; found: C 53.43%, H 3.26%, N 0.00%.



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Saturday, 16 September 2017

Endo-4,7-bis(hydroxymethyl)hexahydro-1H-4,7-epoxyisoindole-1,3(2H)-dione (endo-4,7- bis(hydroxymethyl)norcantharimide)






Endo-4,7-bis(hydroxymethyl)hexahydro-1H-4,7-epoxyisoindole-1,3(2H)-dione (endo-4,7- bis(hydroxymethyl)norcantharimide), 4 (method A)

Endo-4,7-bis(hydroxymethyl)norcantharimid-5-ene (120 mg, 0.53 mmol) was dissolved in water (3 mL), Pd/C 10% was added (15 mg) and reaction mixture was placed under hydrogen atmosphere for 8 h at 24 °C. Catalyst was filtered off and washed thoroughly with water (3 × 3 mL), filtrate was evaporated under reduced pressure. Target compound 4 was obtained as white solid, yield 87% (110 mg).

1H NMR (D2O) = 3.76 (s, 4H), 3.46 (s, 2H), 1.61-1.72 (m, 4H);

1H NMR (DMSO-d6) = 11.10 (s, 1H), 5.08 (s, 2H), 3.66 (s, 4H), 3.37 (s, 2H), 1.71 (m, 2H), 1.49 (m, 2H);

13C NMR (D2O) = 179.0, 88.8, 60.7, 52.3, 27.0 ppm.

m/z HRMS (ESI) Calcd. for C10H13NO5 [M+Na]: 250.0686. Found 250.0696.

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

 Author affiliations
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2,5-Bis(ethoxymethyl)furan

2,5-Bis(ethoxymethyl)furan, 6

1H NMR (CDCl3) = 6.20 (s, 2H), 4.36 (s, 4H), 3.47 (q, 4H, J = 7.1 Hz), 1.16 (t, 6H, J = 7.1 Hz);


13C NMR (CDCl3) = 150.9, 109.7, 65.7, 64.7, 15.1 ppm



PREDICTS





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

 Author affiliations
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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

 Author affiliations

Abstract

The first synthesis of tricyclic compounds from biobased 5-hydroxymethylfurfural (HMF) is described. The Diels–Alder reaction was used to implement the transition from HMF to a non-planar framework, which possessed structural cores of naturally occurring biologically active compounds and building blocks of advanced materials. A one-pot, three-step sustainable synthesis in water was developed starting directly from HMF. The reduction of HMF led to 2,5-bis(hydroxymethyl)furan (BHMF), which could be readily involved in the Diels–Alder cycloaddition reaction with HMF-derived maleimide, followed by hydrogenation of the double bond. The described transformation was diastereoselective and proceeded with a good overall yield. The applicability of the chosen approach for the synthesis of analogous structures containing amine functionality on the side chain was demonstrated. To produce the target compounds, only platform chemicals were used with carbohydrate biomass as the single carbon source.

Endo-4,7-bis(hydroxymethyl)-3a,4,7,7a-tetrahydro-1H-4,7-epoxyisoindole-1,3(2H)-dione (endo-4,7-bis(hydroxymethyl)norcantharimid-5-ene), 3

1H NMR (DMSO-d6) = 10.82 (s, 1H), 6.37 (s, 2H), 5.11 (t, 2H, J = 5.7 Hz), 3.97 (dd, 2H, J = 5.7 Hz, 12.8 Hz), 3.84 (dd, 2H, J = 5.7 Hz, 12.8 Hz), 3.44 (s, 2H);
13C NMR (DMSO-d6) = 176.9, 136.0, 92.1, 59.8, 48.8 ppm.
m/z HRMS (ESI) Calcd. for C10H11NO5 [M+Na]: 248.0529. Found 248.0536.
STR7
str4 str6
1H NMR PREDICT

str4
str4 str6
13C NMR PREDICT

str4 str6
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O=C1NC(=O)[C@H]3[C@@H]1[C@]2(C=C[C@]3(CO)O2)CO