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DR ANTHONY MELVIN CRASTO,WorldDrugTracker, helping millions, A 90 % paralysed man in action for you, I am suffering from transverse mylitis and bound to a wheel chair, With death on the horizon, nothing will not stop me except God................DR ANTHONY MELVIN CRASTO Ph.D ( ICT, Mumbai) , INDIA 25Yrs Exp. in the feld of Organic Chemistry,Working for GLENMARK GENERICS at Navi Mumbai, INDIA. Serving chemists around the world. Helping them with websites on Chemistry.Million hits on google, world acclamation from industry, academia, drug authorities for websites, blogs and educational contribution

Saturday, 20 December 2014

VERBENOL

Sample Description:

Molecular Formula: C₁₀H₁₆O
Molecular Weight: 152.233

InChI=

1/C10H16O/c1-6-4-9(11)8-5-7(6)10(8,2)3/h4,7-9,11H,5H2,1-3H3

IUPAC Name:

4,6,6-Trimethylbicyclo[3.1.1]hept-3-en-2-ol

CAS Number: 18881-04-4
PubChem: 61126
NMRShiftDB: 10021322
Spectrometer: Varian INOVA 500 MHz
Solvent: CDCl₃
Sample Concentration: 8 mg

Properties calculated from structure

Property	Value
Formula	C₁₀H₁₆O
Weight	152.233 [g/mol]
Complexity	214.91
XLogP	2.12
TPSA	20.23
#HDonors	1
#HAcceptors	1
Gibbs Energy	-42.9 [kcal/mol]
¹H NMR spectrum	Predict NMR spectrum (requires installed Java plugin) Predict NMR spectrum (requires HTML5 compatible browser)
¹³C NMR spectrum	Predict NMR spectrum (requires HTML5 compatible browser)
Isotopic distribution	Predict Isotopic distribution

1D Proton Spectrum (TMS Resonances Subtracted):

2D HMQC Spectrum:

Determined HMQC Correlations:

Top 10 FindIt Molecular Structures Consistent With Proton and Protonated Carbon (HMQC) Resonances:

The correct structure is at position 1.


 Best 10 structures in decreasing rating (structure ID shown in parentheses):
    1: 0.892462 (   61126)    2: 0.792875 (  421322)    3: 0.786969 (  118088)
    4: 0.782868 (  433073)    5: 0.782421 (  556905)    6: 0.776775 (  247518)
    7: 0.775072 (  282018)    8: 0.774000 (   72421)    9: 0.773790 (   91238)
   10: 0.773789 (  247514)

2D Phase Sensitive HMBC Spectrum:

AssembleIt HSQC (HMQC) & HMBC Derived Carbon-Carbon Correlations:

AssembleIt Derived Structure With NMRgraph Added Likely Oxygen Atoms:

Most likely structure (out of 4 possible ones) by agreement with carbon chemical shift prediction

MASS SPECTRUM

Comments:

Verbenol is a monoterpenoid pheromone.

The verbenol datasets were our first application of using indirect detection spectra. We used to base structure elucidations on a 1D carbon and a 2D INADEQUATE spectrum. Indirect detection methods gain an order of magnitude in sensitivity. But we continued to use the 1D carbon spectrum which is the least sensitive spectrum by now. Eliminating it completes our goal of indirect detection. Several insights result:

It greatly simplifies the structure elucidation when all spectra are acquired with consistent referencing (not the case for this sample). The next best approach is to use the 1D carbon spectrum to adjust the carbon referencing of all spectra. Here it was necessary to use the exhaustive HSQC and HMBC F1 mapping results for referencing corrections. This is tedious and acquiring datasets with consistent referencing is preferable.

Strong ridges at the TMS (0 ppm) and the three methyl carbon frequencies show in the regular HMBC. Adjustment of the single "Ridge" parameter excludes ridge misinterpretations as shown. It would be preferable to acquire this spectrum with Pulse Field Gradient support to simplify the spectral analysis.

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3,5-diprenyl-4-hydroxycinnamic acid, or Artepillin C

http://www.scielo.br/scielo.php?script=sci_arttext&pid=S1413-70542011000600002

One- and two-dimensional NMR analyses carried out in CD₃OD confirmed this result, since the data obtained were consistent with the structure of 3,5-diprenyl-4-hydroxycinnamic acid, also known as artepillin C (Figure 1): ¹H NMR (500 MHz, CD₃OD): 7.14 (1H, s, H-2), 7.53 (1H, d, J=16.0 Hz, H-7), 6.19 (1H, d, J=16.0 Hz, H-8), 3.32 (2H, br.d, J=7.3 Hz, H-1' and 1''), 5.32 (2H, br.t, J=7.3 Hz, H-2' and 2''), 1.76 (2H, s, H-4' and 4''), 1.72 (2H, s, H-5' and 5''). ¹³C NMR (125 MHz, CD₃OD): 127.5 (C-1), 128.4 (C-2 and 6), 130.2 (C-3 and 5), 156.3 (C-4), 147.2 (C-7), 115.4 (C-8), 171.2 (C-9), 29.5 (C-1' and 1''), 123.3 (C-2' and 2''), 134.0 (C-3' and 3''), 25.9 (C-4' and 4''), 17.9 (C-5' and 5''). Since no NMR spectrum of artepillin C dissolved in CD₃OD was found in the literature, ¹H NMR (400 MHz) analysis was also carried out in CDCl₃and the spectrum obtained was in complete agreement with data given in the literature (AGA et al., 1994; PARK et al., 2004).

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Multifunctional indenes

Figure 1: Key NMR responses for compounds 17, 19 and 23: 1D NOESY experiments.

Beilstein J. Org. Chem. 2011, 7, 1739–1744.

http://www.beilstein-journals.org/bjoc/single/articleFullText.htm?publicId=1860-5397-7-204

Scheme 1: Retrosynthetic pathways to 3,5-disubstituted indenes bearing two functional groups: Indenylsulfonamides 1.

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WO2008059370A2

Example 11 : Λ/-(1-(1-(2-hvdroxyethvh-5-methyl-1H-pyrazol-4-vhethvh-2- (2,2.2-trifluoro-1.1 -dimethylethvOαuinoline-β-carboxamtde

To a solution of Example 10 (23 mg, 0.05 mmol) in THF (3 ml) was added LiBH₄ powder (3.25 mg, 0.15 mmol) at rt, and the resulting mixture was heated at 65 ⁰C, then MeOH (3 drops) was added and the resulting mixture was heated at the same temperature for 60 min. After being cooled to rt, the reaction mixture was quenched by addition of sat. NH₄CI aq. and the aqueous layer was extracted with AcOEt 3 times. The combined organic extracts were washed with water and brine successively, dried over Na₂SO₄ and concentrated in vacuo. The crude material was purified by HPLC (column: MS C 30 x 50 mm, acetonitrile: 0.01 % NH₃ aq =96:4 to 4:96 as eluent) to give the title compound as a white solid (16.6 mg, 77% yield). ¹H NMR (300 MHz, DMSO-Of₆) δ 1.50 (3H, d, J = 6.0 Hz), 1.71 (6H₁ s), 2.26 (3H, s), 3.67 (2H, dd, J = 6.0, 12.0 Hz)₁ 4.03 (2H₁ t, J = 6.0 Hz), 4.84 (1 H, t, J = 6.0 Hz)₁ 5.14-5.24 (1 H, m), 7.46 (1 H₁ s), 7.87 (1 H₁ d, J = 9.0 Hz)₁ 8.07 (1H₁ d, J = 9.0 Hz), 8.19-8.23 (1 H₁ m), 8.50-8.53 (2H₁ m), 8.85 (1 H₁ brd, J = 6.0 Hz). MS (ESI) m/z 433 (M - H)^" , 435 (M + H)⁺.

http://www.google.com/patents/WO2008059370A2?cl=en

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5-(6-Methoxy-1H-imidazo[4,5-c]pyridin-1-yl)-3-{[2-(trifluoromethyl)benzyl]oxy}thiophene-2-carboxamide

5-(6-Methoxy-1H-imidazo[4,5-c]pyridin-1-yl)-3-{[2-(trifluoromethyl)benzyl]oxy}thiophene-2-carboxamide

[0124]

A suspension of 140 mg of an isomeric mixture of methyl 5-(6-methoxy-3H-imidazo[4,5-c]pyridin-3-yl)-3-{[2-(trifluoromethyl)benzyl]oxy}thiophene-2-carboxylate and methyl 5-(6-methoxy-1H-imidazo[4,5-c]pyridin-1-yl)-3-{[2-(trifluoromethyl)benzyl]oxy}thiophene-2-carboxylate (compounds B6a and B6b) in 20 ml of a saturated solution of ammonia in methanol is stirred in a microwave vial at 130 °C for 5 h in the microwave cavity. The reaction mixture is concentrated to dryness, the residue dissolved in 4 ml acetonitrile and 3 ml acidic buffer (KH₂PO₄, pH=2) and the isomers are separated and purified by preparative HPLC (acidic buffer/acetonitrile, 7/3 (v/v)). The acetonitrile is removed under vacuum and the aqueous solution is treated with NH₄OH until pH 8-9 is reached. The aqueous solution is extracted with dichloromethane three times and the combined organic layers are dried and concentrated to dryness under vacuum to yield the title compound.
The structural assignment of the regioisomer is unequivocally established by two-dimensional ¹H NMR experiments (NOESY, COSY).
NOE-crosspeaks are detected between H-8 and H-7, H-7 and H-4', H-4' and H-2:

¹H NMR (400 MHz, D₆-DMSO): δ = 3.94 (s, 3H, H-8), 5.56 (s, 2H, H-9), 6.79 (bs, 1 H, H-18), 7.11 (s, 1 H, H-7), 7.64-7.70 (m, 3H, including s, 1 H, H-4' at 7.68; bs, 1 H, H-18 and 1 H out of H-12, H-13, H-14, H-15), 7.77-7.86 (m, 3H, three H's out of H-12, H-13, H-14, H-15), 8.64 (s, 1 H, H-2), 8.69 (s, 1 H, H-4). MS (MH⁺ found) = 449.1

SEE

http://www.google.com/patents/EP2017277A1?cl=en

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Carbamazepine

see
http://www.scielo.br/scielo.php?script=sci_arttext&pid=S0100-40422012000700033

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Me

DR ANTHONY MELVIN CRASTO Ph.D ( ICT, Mumbai), INDIA, worlddrugtracker, 29Yrs Exp. in the field of Organic Chemistry,Working for GLENMARK PHARMA at Navi Mumbai, INDIA. Serving chemists around the world. Helping them with websites on Chemistry.Million hits on google, world acclamation from industry, academia, drug authorities for websites, blogs and educational content...........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. सुकून उतना ही देना प्रभू, जितने से जिंदगी चल जाये। औकात बस इतनी देना,कि औरों का भला हो जाये।

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Saturday, 20 December 2014

VERBENOL

VERBENOL

Sample Description:

Properties calculated from structure

1D Proton Spectrum (TMS Resonances Subtracted):

2D HMQC Spectrum:

Determined HMQC Correlations:

Top 10 FindIt Molecular Structures Consistent With Proton and Protonated Carbon (HMQC) Resonances:

2D Phase Sensitive HMBC Spectrum:

AssembleIt HSQC (HMQC) & HMBC Derived Carbon-Carbon Correlations:

AssembleIt Derived Structure With NMRgraph Added Likely Oxygen Atoms:

MASS SPECTRUM

Comments:

amcrasto@gmail.com

3,5-diprenyl-4-hydroxycinnamic acid, or Artepillin C

amcrasto@gmail.com

Multifunctional indenes

amcrasto@gmail.com

WO2008059370A2

amcrasto@gmail.com

5-(6-Methoxy-1H-imidazo[4,5-c]pyridin-1-yl)-3-{[2-(trifluoromethyl)benzyl]oxy}thiophene-2-carboxamide

amcrasto@gmail.com

Carbamazepine

amcrasto@gmail.com

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