3-Methyl-lH-pyrazolo[3,4b]pyridine.

3-Methyl-lH-pyrazolo[3,4b]pyridine.

A solution of l-(2-chloropyridin-3-yl)ethanone (22 g, 0.1415 mol) and hydrazine hydrate 98% (113 g, 2.21 mol) in ethanol (300 mL) was refluxed for 12 h. About 80% of the ethanol was distilled off under reduced pressure using a rotary evaporator. The residue was allowed to come to room temperature. The precipitated solid was filtered and washed with water. The product was dried at 90 ⁰C to constant weight (16 g, 85%) mp 152-154 ⁰C. ¹H NMR (CDCl₃) 8.62 (dd, J = 4.5 and 1.4 Hz, 1 H), 8.08 (dd, J = 8.0 and 1.4 Hz, 1 H), 7.15 (dd J = 8.0 and 4.5 Hz, 1 H), 2.64 (s, 3 H). MS (FAB) m/z: 133 (M⁺ +1).

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1-(2,4-Dichlorobenzyl)-lH-pyrazolor3,4blpyridine-3-carboxylic Acid

l-(2,4-Dichlorobenzyl)-lH-pyrazolor3,4blpyridine-3-carboxylic Acid

lH-Pyrazolo[3,4b]pyridine-3-carboxylic acid methyl ester (8 g, 0.0452 mol) was suspended in acetonitrile (200 mL) and the resulting suspension was stirred under heating for 10 min. in order to homogenize the solution. Potassium carbonate (31.2 g, 0.226 mol) was then added in one lot, followed by the addition of the tetrabutylammonium iodide (0.08 g, catalytic) and 2,4-dichlorobenzyl chloride (10.6 g, 0.0543 mol). The reaction mixture was heated to reflux for 2 h under good stirring. The reaction progress was monitored by TLC. After completion of the reaction, the mixture was cooled to room temperature and potassium carbonate was filtered off. Acetonitrile was distilled off under reduced pressure to afford the crude benzylated product. The crude product was purified using column chromatography (silica gel, eluent started with hexane then 8:2 hexane/ethyl acetate) to yield the pure product as white crystals (11 g, 73%) mp 135-136 ⁰C. 

¹H NMR (CDCl₃) 8.04 (dd, J = 4. 5 and 1.6 Hz, 1 H), 8.58 (dd, J = 8.1 and 1.6 Hz, 1 H), 7.45 (d, J = 2.0 Hz, 1 H), 7.36 (dd, J = 8.1 and 4.5 Hz, 1 H), 7.10 (dd, J = 8.3 and 2.0 Hz, 1 H), 6.72 (d, J = 8.3 Hz, 1 H ), 5. 92 (s, 2 H), 4.06 (s, 3 H). 

MS (FAB) m/z: 336 (M⁺+ 1).

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1H-Pyrazolo[3,4b]pyridine-3-carboxylic Acid.

lH-Pyrazolo[3,4b]pyridine-3-carboxylic Acid.

KMnO₄ZNaOHZH₂O

reflux, 2 h

Sodium hydroxide (35 g, 0.88 mol) was dissolved in water (800 mL), then 3- methyl-lH-pyrazolo[3,4b]pyridine (16 g, 0.12 mol) was added to a solution of sodium hydroxide and stirred at room temperature for 10 minutes. The reaction mixture was heated to 80 ⁰C. Under good stirring potassium permanganate solution (68.5 g, 0.433 mol OfKMnO₄ in 300 mL water) was slowly added dropwise over a period of 2 h, keeping the oil bath temperature at 100 ⁰C. After completing the addition of potassium permanganate, the reaction mixture was further heated for 1 hr. The progress of the reaction was monitored by TLC. The reaction mixture was cooled to 70-80 ⁰C and the byproduct manganese dioxide was filtered off. The manganese dioxide cake was washed with hot water. The main filtrate and the washings were combined and acidified to pH 2 with concentrated sulfuric acid. The water was then distilled off under reduced pressure using a rotary evaporator. The yellow solid obtained was a mixture of the desired IH- pyrazolo[3,4b]pyridine-3-carboxylic acid, sodium sulfate and potassium sulfate (95 g). This mixture of solids was taken without purification to the next step. A small sample was purified by column chromatography for analytical purposes to afford white crystals mp 175-176 ⁰C. 

¹H NMR (CDCl₃) 8.28 (dd, J = 4.9 and 1.6 Hz, 1 H), 7.82 (dd, J = 7.5 and 1.6 Hz, 1 H), 7.39 (dd J = 7.5 and 4.9 Hz, 1 H). 

MS 9FAB) m/z: 147 (M⁺ + 1)

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सुकून उतना ही देना प्रभू, जितने से

जिंदगी चल जाये।

औकात बस इतनी देना,

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1-(2-Chloropyridin-3-yl)ethanol

Step 1 : l-(2-Chloropyridin-3-yl)ethanol.

Dry THF (400 mL) and n-butyllithium (1.6 M in hexane, 63 mL, 0.1 mol) were introduced into a IL flask under nitrogen at -70⁰C. A solution of dry diisopropylamine (10.1 g, 0.1 mol) in THF (25 mL) was added dropwise to the mixture at -70 ⁰C. The mixture was then kept for 1 h at 0 ⁰C and then cooled to -70 ⁰C. A solution of 2- chloropyridine (11.3 g, 0.1 mol) in THF (25 mL) was added dropwise to the mixture at - 70 ⁰C and the mixture was stirred for 3 h at this temperature. A solution of acetaldehyde (4.85 g, 0.11 mol) in dry THF (50 mL) was then added dropwise and the mixture was kept for 3 h at -70 ⁰C. A solution of water (4 mL) in THF (40 mL), acidified by a few drops of concentrated hydrochloric acid, was added to the mixture at -40 ⁰C and then water (200 mL) was introduced at -10 ⁰C. Extraction with diethyl ether (3x150 mL), drying over anhydrous sodium sulfate, and evaporation gave a crude product, which was purified by column chromatography to yield an oil (10 g, 64%). 
*1H NMR (CDCl₃) 8.15 (dd, J = 5 and 2 Hz, 1 H), 7.95 (dd, J = 8 and 2 Hz, 1 H), 7.20 (dd, J = 8 and 5 Hz, 1 H), 5.15 (d, J = 7 Hz, 1 H), 3.90 (s, 1 H), 1.45 (d, J = 7 Hz, 3 H).

* NMR values reported in Journal of Chemical Society Perkin Trans 1 : Organic and Bio-organic Chemistry, 1990, 9, 2409-2415.

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The title compound was synthesized by opening the epoxide of benzyl 2,3-anhydro-β-L-ribopyranoside with 3,4,5-trimethoxybenzylamine (Scheme 1). The three broad peaks in the 1 H-NMR due to one –NH at δ 2.20 ppm, and two –OH at δ 5.00 ppm and 5.26 ppm, disappeared upon D2O exchange. The chemical shifts of the sugar hydrogens, along with COSY and HMBC were used to assign C7, C1″, C2″, C3″, C4″, C5″ and C7′ atoms. The coupling constant between H-1″ and H-2″ on the sugar ring was found to be 7.98 Hz, indicating that the protons at the 1- and 2-positions were in axial positions and that the molecule exists in solution in 1 C4 conformation (Scheme 1). The coupling constant was similar to related analogs [14,15]. The coupling constant between H-2” and H-3” was found to be 9.12 Hz. The coupling constant between the pro-R and pro-S hydrogens on C7 was found to be 12.24 Hz. The 13C had five pairs of atoms with the same chemical shift. There were three pairs of carbon atoms on the 3,4,5-trimethoxybenzyl ring ( two ortho- and two meta-, and two equivalent methoxy groups) that had similar chemical shifts. On the benzyl group, chemical shifts of two pairs of carbon atoms (two ortho- and two meta-) were observed.
PREPN

Benzyl 2,3-anhydro-β-L-ribopyranoside (1) was obtained from L-arabinose in five steps using a previously reported synthetic route [14]. To a mixture of benzyl 2,3-anhydro-β-L-ribopyranoside 1 (0.15 g, 0.68 mmol) and 3,4,5-trimethoxybenzylamine 2 (180 mL, 0.91 mmol) was added ethyl alcohol (3 mL). After refluxing the mixture for 16 h and cooling at room temperature for 12 h, white crystals (needles) formed. Recrystallization from hexane/ethyl acetate mixture (3:2, v/v) produced a pure compound (0.206 g, 72%,
m.p. 158–160 °C);
[α]D 26 +50° (c 1, CHCl3).
C22H29NO7 Calculated: C 62.99; H, 6.97; N, 3.34; O, 26.70 Found: C 62.89; H, 7.01; N, 3.29; O, 26.65

1 H-NMR (400 MHz, Me2SO-d6)
δ 2.20 (bs, 1H, –NH),
2.41 (t, J = 9.12, 7.98 Hz, 1H, H-3),
3.21 (m, 2H),
3.45 (bs, 1H),
3.65 (s, 3H, –OCH3),
3.75 (b, 1H),
3.80 (s, 6H, 2-OCH3),
3.97 (m, 2H),
4.31 (d, J = 7.98 Hz, 1H, H-1),
4.61 (d, J = 12.24 Hz, 1H, –OCH2Ar),
4.80 (d, J = 12.24 Hz, 1H, –OCH2Ar),
5.00 (bs, 1H, –OH), 5.26 (bs, 1H, –OH).


13C-NMR (100 MHz, Me2SO-d6),
δ 53.22 (C-7′),
56.61 (–OCH3),
60.81 (–OCH3),
65.11 (C-3″),
67.37 (C-5″),
70.14 (C-4″),
70.41 (C-7),
73.00 (C-2″),
103.90 (C-1″),
105.80, 128.23, 128.40, 129.00, 136.80, 138.23, 138.93, 153.52.

 Nmr predict

Molbank 2013, 2013(1), M793; doi:10.3390/M793

Benzyl 3-deoxy-3-(3,4,5-trimethoxybenzylamino)-β-L-xylopyranoside

Fulgentius Nelson Lugemwa 

Department of Chemistry, Pennsylvania State University-York, 1031 Edgecomb Avenue, York, PA 17403, USA

http://www.mdpi.com/1422-8599/2013/1/M793

//////epoxide ring-opening, 3,4,5-trimethoxybenzylamine, benzyl 2,3-anhydro-β-L-ribopyranoside

3 - [ 1 -(2,4-Dichlorobenzyl)-6-trifluoromethyl- 1 H-indazol-3 -yl] -acrylic acid ethyl ester.

Step 8 : 3 - [ 1 -(2,4-Dichlorobenzyl)-6-trifluoromethyl- 1 H-indazol-3 -yl] -acrylic acid ethyl ester.

1 -(2,4-Dichlorobenzyl)-6-trifluoromethyl- 1 H-indazole-3 -carbaldehyde (2.0 g, 0.00536 mol) was dissolved in CH₂Cl₂ (50 mL) and Wittig reagent (carbethoxymethylene) triphenylphosphorane (1.06 g, 0.0536 mol) was added to the solution. The homogeneous reaction mixture was heated to reflux in an oil bath for 12 h. The reaction progress was monitored by TLC. The reaction mixture was cooled to room temperature and worked up by quenching into water and separating the organic layer. Removal of the CH₂Cl₂ yielded the crude product, which was purified by column chromatography to yield the pure product (2.25 g, 95%) as a white solid, mp 186-188 ⁰C. 

¹H NMR (CDCl₃) 8.08 (d, J = 8.5 Hz, 1 H), 7.99 (d, J = 16.2 Hz, 1 H), 7.74 (s, 1 H), 7.52 (d, J = 8.5 Hz, 1 H), 7.47 (d, J = 2.0 Hz, 1 H), 7.16 (dd, J = 8.3 and 2.0 Hz, 1 H), 6.84 (d, J = 8.3 Hz, 1 H), 6.82 (d, J = 16.2 Hz, 1 H), 5.72 (s, 2 H), 4.32 (q, J = 7.1 Hz, 2 H), 1.38 (t, J = 7.1 Hz, 3 H). 

MS (FAB) m/z: 443 (M⁺ + 1).

see
https://www.google.im/patents/WO2011005759A2?cl=en




 सुकून उतना ही देना प्रभू, जितने से जिंदगी चल जाये। औकात बस इतनी देना, कि औरों का भला हो जाये।
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सुकून उतना ही देना प्रभू, जितने से
जिंदगी चल जाये।
औकात बस इतनी देना,
कि औरों का भला हो जाये।
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