Absolute Configuration of (+)-Erythro-Mefloquine

 

The absolute configuration of (+)-erythro-mefloquine has been confirmed by X-ray crystallography, CD spectroscopy, and molecular modeling
Read more
http://www.chemistryviews.org/details/ezine/4948391/Absolute_Configuration_of_-Erythro-Mefloquine.html

Absolute Configuration and Antimalarial Activity of erythro-Mefloquine Enantiomers,
Alexandra Dassonville-Klimpt, Christine Cézard, Catherine Mullié, Patrice Agnamey, Alexia Jonet, Sophie Da Nascimento, Mathieu Marchivie, Jean Guillon, Pascal Sonnet,
ChemPlusChem 2013.
DOI: 10.1002/cplu.201300074

The Absolute Configuration of (+)- and (−)-erythro-Mefloquine,
Michael Müller, Claudia M. Orben, Nina Schützenmeister, Manuel Schmidt, Andrei Leonov, Uwe M. Reinscheid, Birger Dittrich, Christian Griesinger,
Angew. Chem. Int. Ed. 2013.
DOI: 10.1002/anie.201300258

VALSARTAN SPECTRAL DATA

 
VALSARTAN

mp 114–118 °C; 

¹H NMR (400 MHz, DMSO-d₆): δ 12.6 (brs, 1H), 7.72 (m, 4H), 7.24 (m, 1H), 7.15 (m, 2H), 6.94 (m, 1H), 4.58 (m, 1H), 4.40 (m, 1H), 3.33 (m, 1H), 2.25 (m, 1H), 1.52 (m, 6H), 0.9 (m, 3H), 0.84 (m, 3H), 0.74 (m, 3H); 


¹³C NMR (100 MHz, DMSO-d₆): δ 174.0, 172.4, 171.8, 141.7, 138.2, 131.54, 131.1, 131.0, 129.3,128.8, 128.2, 127.4, 126.7, 70.3, 63.4, 49.9, 32.9, 28.05, 27.3, 22.2, 20.6, 14.2; 

ESIMS: m/z calcd [M]⁺: 435; found: 436 [M+H]⁺; HRMS (ESI): m/z calcd [M]⁺: 435.5187; found: 435.5125 [M]<sup>+




US 7439261 B2
1H-NMR (CDCl₃) (0.80-1.15 (m, 9H); 1.20-1.50 (m, 2H); 1.60-1.80 (m, 2H); 2.60 (t, 2H); 2.65-2.80 (m, 2H), 3.70 (d, 1H), 4.10 (d, 0.3 H), 4.30 (d, 0.7 H), 4.90 (d, 0.7H), 5.2 (d, 0.3H); 7.00 (d, 0.3H); 7.10-7.20 (m, 4H), 7.40-7.60 (m, 3H), 7.85 (d, 0.7 H).



SHORT DESCRIPTION</sup>

Valsartan, N-(1-oxopentyl)-N-[[2′-(1H-tetrazol-5-yl)[1,1′-biphenyl]-4-yl]methyl]-L-valine, is a known anti-hypertensive agent having the following formula (I):

Valsartan and its preparation are disclosed in U.S. Pat. No. 5,399,578, in particular in Example 16. One of the synthetic routes according to U.S. Pat. No. 5,399,578 can be schematically represented as follows:

The synthetic pathway comprises various steps, among which:

• • coupling of compound (3) with 2-chlorobenzonitrile to obtain compound (4),
  • radicalic bromination of compound (4) to give compound (5),
  • transformation of the brominated derivative (5) into the respective aldehyde derivative (6),
  • reductive alkylation of compound (6) to obtain intermediate (8),
  • acylation of compound (8) to obtain intermediate (9),
  • conversion of the cyano group to the tetrazole group to afford intermediate (10),
  • deprotection of the carboxylic group by hydrogenolysis to obtain valsartan.

• It is marketed as the free acid under the name DIOVAN. DIOVAN is prescribed as oral tablets in dosages of 40 mg, 80 mg, 160 mg and 320 mg ofvalsartan.
• [0004]
  Valsartan and/or its intermediates are disclosed in various references, including: U.S. Pat. Nos. 5,399,578 ,5,965,592 , 5,260,325 , 6,271,375 , WO 02/006253 , WO 01/082858 , WO 99/67231 , WO 97/30036 , Peter Bühlmayer, et. al., Bioorgan. & Med. Chem. Let., 4(1) 29-34 (1994), Th. Moenius, et. al., J. Labelled Cpd. Radiopharm., 43(13) 1245 - 1252 (2000), and Qingzhong Jia, et. al., Zhongguo Yiyao Gongye Zazhi, 32(9) 385-387 (2001), all of which are incorporated herein by reference.
• [0005]
  Valsartan is an orally active specific angiotensin II antagonist acting on the AT1 receptor subtype. Valsartan is prescribed for the treatment of hypertension. U.S. Pat. No. 6,395,728 is directed to use of valsartan for treatment of diabetes related hypertension. U.S. Pat. Nos. 6,465,502 and 6,485,745 are directed to treatment of lung cancer with valsartan. U.S. Pat. No. 6,294,197 is directed to solid oral dosage forms of valsartan

GOOD ARTICLES

http://users.uoa.gr/~tmavrom/2009/valsartan2009.pdf

http://www.acgpubs.org/JCM/2009/Volume%203/Issue%201/JCM-0908-14.pdf

https://www.beilstein-journals.org/bjoc/single/printArticle.htm?publicId=1860-5397-6-27 REPORTS
 mp 114–118 °C; ¹H NMR (400 MHz, DMSO-d₆): δ 12.6 (brs, 1H), 7.72 (m, 4H), 7.24 (m, 1H), 7.15 (m, 2H), 6.94 (m, 1H), 4.58 (m, 1H), 4.40 (m, 1H), 3.33 (m, 1H), 2.25 (m, 1H), 1.52 (m, 6H), 0.9 (m, 3H), 0.84 (m, 3H), 0.74 (m, 3H); ¹³C NMR (100 MHz, DMSO-d₆): δ 174.0, 172.4, 171.8, 141.7, 138.2, 131.54, 131.1, 131.0, 129.3,128.8, 128.2, 127.4, 126.7, 70.3, 63.4, 49.9, 32.9, 28.05, 27.3, 22.2, 20.6, 14.2; ESIMS: m/z calcd [M]⁺: 435; found: 436 [M+H]⁺; HRMS (ESI): m/z calcd [M]⁺: 435.5187; found: 435.5125 [M]⁺

Valsartan 

Structural formula

UV - Spectrum

Conditions : Concentration - 1 mg / 100 ml
The solvent designation schedule	methanol	water	0.1М HCl	0.1M NaOH
maximum absorption	249 nm	250 nm	248 nm	251 nm
	309	302	289	311
e	13400	13100	12600	13500

IR - spectrum

Wavelength (μm)
Wave number (cm -1 )

NMR spectrum

references

• UV and IR Spectra. H.-W. Dibbern, R.M. Muller, E. Wirbitzki, 2002 ECV
• NIST/EPA/NIH Mass Spectral Library 2008
• Handbook of Organic Compounds. NIR, IR, Raman, and UV-Vis Spectra Featuring Polymers and Surfactants, Jr., Jerry Workman. Academic Press, 2000.
• Handbook of ultraviolet and visible absorption spectra of organic compounds, K. Hirayama. Plenum Press Data Division, 1967.

<sup>CLIP





Scheme 2: (a) Et3N, CH2Cl2, 0 °C, 95%; (b) NaH, THF, 70%; (c) n-BuLi, 25 °C, THF, anhyd ZnCl2, −20 °C, Q-phos, Pd(OAc)2, 75 °C, 2 h, 80%; (d) 3 N NaOH, MeOH, reflux, 90%.

http://www.beilstein-journals.org/bjoc/single/articleFullText.htm?publicId=1860-5397-6-27

valsartan 8; mp 114–118 °C; 1H NMR (400 MHz, DMSO-d6): δ 12.6 (brs, 1H), 7.72 (m, 4H), 7.24 (m, 1H), 7.15 (m, 2H), 6.94 (m, 1H), 4.58 (m, 1H), 4.40 (m, 1H), 3.33 (m, 1H), 2.25 (m, 1H), 1.52 (m, 6H), 0.9 (m, 3H), 0.84 (m, 3H), 0.74 (m, 3H); 13C NMR (100 MHz, DMSO-d6): δ 174.0, 172.4, 171.8, 141.7, 138.2, 131.54, 131.1, 131.0, 129.3,128.8, 128.2, 127.4, 126.7, 70.3, 63.4, 49.9, 32.9, 28.05, 27.3, 22.2, 20.6, 14.2; ESIMS: m/z calcd [M]+: 435; found: 436 [M+H]+; HRMS (ESI): m/z calcd [M]+: 435.5187; found: 435.5125 [M]+












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Video tutorial on spectroscopy

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IB Chemistry Atomic Absorption Spectroscopy, Nuclear Magnetic Resonance Spectroscopy and NMR from Lawrence Kok

SPECTROSCOPY DATA of ASPIRIN

 Dear blog reader , this post is for brushing up our fundamentals of spectroscopy using simple molecules like aspirin
text may be less but graphs are educative. one can browse through this to brush up




Product Name: Acetylsalicylic acid CAS:50-78-2










1H NMR



 

    Assign.     Shift(ppm)

      A            11.
      B             8.125
      C             7.624
      D             7.356
      E             7.142
      F             2.352
  ABOVE IS PROTON NMR OF ASPIRIN AND ITS INTERPRETATION

abelled.



The peaks I have are:

2.30ppm (I this is a singlet and would be F)
7.07ppm (I think this is E)
7.29ppm (I think this is D)
7.53ppm (I think this is C)
8.05ppm (I think this is B)
11.44ppm (this is a singlet and would be A)


For B,C,D,E I need to say what kind of splitting pattern there would be and how many coupling constants are present and there approximate value. I think I know the assignments of them but I don't know the splitting pattern or coupling constants.

Would E and B be doublet of doublets because they couple with D and C so they would have ortho and meta coupling?

Would D and C be coupling with each other and B and E so would they be doublet of doublets of doublets, with two ortho and one meta coupling?

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 BELOW IS IR OF ASPIRIN KBR DISC









IR in nujol mull

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MASS SPECTRUM







above is mass spectrum of aspirin

o-acetoxybenzoic acid
C9H8O4              (Mass of molecular ion:    180)

 Source Temperature: 170 °C
   Sample Temperature: 100 °C
   DIRECT, 75 eV

13 C NMR

 


above is 13 C NMR OF ASPIRIN

50.18 MHz
C9 H8 O4	0.039 g : 0.5 ml CDCl3

 ppm   Int.  Assign.

      170.20   450      1
      169.76   510      2
      151.28   560      3
      134.90   924      4
      132.51  1000      5
      126.17   986      6
      124.01   974      7
      122.26   397      8
       20.99   674      9

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below is Raman spectra of aspirin





NMR INTERPRETATIONS

H-NMR spectral analysis

CAS NO. 50-78-2, Acetylsalicylic acid H-NMR spectral analysis

C-NMR spectral analysis

CAS NO. 50-78-2, Acetylsalicylic acid C-NMR spectral analysis H, H-COSY spectrum In H, H-COSY spectrum are on both axes, the 1 H chemical shifts plotted; In principle, both the axes 1 to see H-NMR spectra. Thus, there is a symmetric to the diagonal diagram. 1 H-NMR spectrum of acetylsalicylic acid Fig.2 H, H-COSY spectrum of acetylsalicylic acid In the spectrum, only the range from 7.0 to 8.2 ppm is applied, because only here HH scalar couplings can be expected. Fig.3 There are two types of signals: Diagonal signals: join the coordinates δ a δ a (in core A), δ b δ b (in core B) ... on, but play no role in the evaluation of the couplings between different cores, since it is only the signal of a nucleus is. The diagonal with all its signals corresponding to the 1D H-NMR spectrum. EXAMPLE Acetylsalicylic acid 7.13 ppm / 7.13 ppm = δ 2 δ 2 (H atom 2) 7.34 ppm / 7.34 ppm = δ 4 δ 4 (H atom 4) 7.61 ppm / 7.61 ppm = δ 3 δ 3 (H atom 3) 8.11 ppm / 8.11 ppm = δ 5 δ 5 (H atom 5) Cross signals: These signals are based on the scalar spin-spin coupling and are suitable for the evaluation of spectra of enormous importance. EXAMPLE Acetylsalicylic acid 7.13 ppm / 7.61 ppm (δ 2 δ 3 ), and 7.61 ppm / 7.13 ppm (δ 3 δ 2 ) - vicinal coupling between the H-atoms 2 and 3 7.34 ppm / 7.61 ppm (δ 4 δ 3 ) and 7.61 ppm / 7.34 ppm (δ 3 δ 4 ) - vicinal coupling between the H-atoms 4 and 3 7.34 ppm / 8.11 ppm (δ 4 δ 5 ) and 8.11 ppm / 7.34 ppm (δ 5 δ 4 ) - vicinal coupling between the H-atoms 4 and 5 In general it can be seen in the COSY spectrum each scalar coupling between two nuclei at four signals (two cross and two diagonal peaks) resulting connected a square; in the following example, the vicinal coupling between the H atoms is highlighted 3 and 4. Fig.4 With good resolution of the COSY spectrum, the coupling constants can be determined from the fine structure of the cross and diagonal signals, but this is rarely done because of the 1-D H-NMR spectra is easily possible. DRUG APPROVALS BY DR ANTHONY MELVIN CRASTO .....FOR BLOG HOME CLICK HERE Join me on Linkedin Join me on Facebook FACEBOOK Join me on twitter      Join me on google plus Googleplus  amcrasto@gmail.com KHAJURAHO INDIA Location of Khajuraho Group of Monuments in India. Location in Madhya Pradesh Khajuraho Group of Monuments - Wikipedia, the free ... en.wikipedia.org/wiki/Khajuraho_Group_of_Monuments The Khajuraho Group of Monuments are a group of Hindu and Jain temples in Madhya Pradesh, India. About 620 kilometres (385 mi) southeast of New Delhi, ... Hotel Chandela - A Taj Leisure Hotel