Tuesday, 31 March 2015

Simple and effective method for two-step synthesis of 2-(1,3-dithian-2-ylidene)-acetonitrile

Simple and effective method for two-step synthesis of 2-(1,3-dithian-2-ylidene)-acetonitrile (75% overall yield) and molecular modeling calculation of the mechanism by B3LYP and the 6-311++G(2df,2p) basis set.

http://dx.doi.org/10.5935/0100-4042.20140308

Publicado online: dezembro 12, 2014

Método alternativo para a síntese e mecanismo de 2-(1,3-ditiano-2-ilideno)-acetonitrila

Marcelle S. Ferreira; José D. Figueroa-Villar*
Quim. Nova, Vol. 38, No. 2, 233-236, 2015
Artigo http://dx.doi.org/10.5935/0100-4042.20140308
*e-mail: jdfv2009@gmail.com
MÉTODO ALTERNATIVO PARA A SÍNTESE E MECANISMO DE 2-(1,3-DITIANO-2-ILIDENO)-ACETONITRILA
Marcelle S. Ferreira e José D. Figueroa-Villar* Departamento de Química, Instituto Militar de Engenharia, Praça General Tiburcio 80, 22290-270
Rio de Janeiro – RJ, Brasil
Recebido em 18/08/2014; aceito em 15/10/2014; publicado na web em 12/12/2014
ALTERNATIVE METHOD FOR SYNTHESIS AND MECHANISM OF 2-(1,3-DITHIAN-2-YLIDENE)-ACETONITRILE. We report an alternative method for the synthesis of 2-(1,3-dithian-2-ylidene)-acetonitrile using 3-(4-chlorophenyl)-3-oxopropanenitrile and carbon disulfide as starting materials. The methanolysis of the intermediate 3-(4-chlorophenyl)-2-(1,3-dithian-2-ylidene)-3- oxopropanenitrile occurs via three possible intermediates, leading to the formation of the product at a 75% overall yield. Molecular modeling simulation of the reaction pathway using B3LYP 6-311G++(2df,2p) justified the proposed reaction mechanism. Keywords: 2-(1,3-dithian-2-ylidene)-acetonitrile; reaction mechanism; methanolysis; molecular modeling.
3-(4-clorofenil)-2-(1,3-ditiano-2-ilideno)-3-oxopropanonitrila (3): Cristal amarelo. Rendimento: 95%, 2,80 g, pf 158-160 °C, lit.21 159-160 °C;
IV (KBr, cm-1): 2198 (CN), 1612 (C=O), 1585, 1560 (aromático), 678 cm -1 (C-S);
1H RMN (300 MHz, CDCl3) δ 2,38 (m, J 6,9, 2H, CH2); 3,01 (t, J 6,6, 2H, SCH2); 3,17 (t, J 7,2 , 2H, SCH2); 7,43 (d, J 8,5, 2H); 7,83 (d, J 8,5, 2H);
13C RMN (75 MHz, CDCl3) δ 23,9 (CH2), 30,4 (SCH2), 104,2 (CCO), 117,5 (CN), 128,9, 130,5, 135,6, 139,2 (aromático), 185,2 (C=CS), 185,4 (CO).
21.......Rudorf, W. D.; Augustin, M.; Phosphorus Sulfur Relat. Elem. 1981, 9, 329.
...........................................
Síntese da 2-(1,3-ditiano-2-ilideno)-acetonitrila (1) Em um balão de fundo redondo de 100 mL foram adicionados 0,400 g (1,4 mmol) de 3-(4-clorofenil)-2-(1,3-ditiano-2-ilideno)-3- -oxopropanonitrila (2) dissolvidos em 15 mL de THF seco, 0,140 g (20 mmol) de sódio e 15 mL de metanol seco sob atmosfera de nitrogênio. A mistura reacional foi mantida sob agitação à 25 °C por 48 h. Em seguida, a mistura reacional foi dissolvida em 30 mL de água destilada e extraída com acetato de etila (3 x 20 mL). A fase orgânica foi seca em sulfato de sódio anidro, filtrada e concentrada a vácuo para se obter o produto bruto, que foi purificado por cromatografia em coluna (silica gel e hexano:acetato de etila 7:3).
2-(1,3-ditiano-2-ilideno)-acetonitrila (1): Cristal branco. Rendimento: 75%, 165 mg, pf. 60-63 °C, lit1 60-62 °C;
1 H RMN (300 MHz, CDCl3) δ 2,23 (m, J 6,8, 2H, CH2); 3,01 (t, J 7,5, 2H, SCH2); 3,06 (t, J 6,9, 2H, SCH2), 5,39 (s, 1H, CH);
13C RMN (75 MHz, CDCl3) δ 22,9 (CH2), 28,7 (SCH2), 28,8 (SCH2), 90,4 (CHCN), 116,3 (CN), 163,8 (C=CS).
1.........Yin, Y.; Zangh, Q.; Liu, Q.; Liu, Y.; Sun, S.; Synth. Commun. 2007, 37, 703.
 Acetonitrile, 1,3-dithian-2-ylidene-

CAS 113998-04-2

  • C6 H7 N S2
  • Acetonitrile, 2-​(1,​3-​dithian-​2-​ylidene)​-
  • 157.26
Melting Point60-62 °C
1H  NMR  predict
2-(1,3-dithian-2-ylidene)-acetonitrile
BR 1H
BR 1H 1
ACTUAL 1H NMR VALUES
1 H RMN (300 MHz, CDCl3)
δ 2,23 (m, J 6,8, 2H, CH2);
3,01 (t, J 7,5, 2H, SCH2);
3,06 (t, J 6,9, 2H, SCH2),
5,39 (s, 1H, CH);
..........................
13C NMR PREDICT
BR 13C
BR 13C 1
ACTUAL 13C NMR VALUE
13C RMN (75 MHz, CDCl3)
δ 22,9 (CH2),
28,7 (SCH2),
28,8 (SCH2),
90,4 (CHCN),
116,3 (CN),
163,8 (C=CS)
COSY NMR PREDICT
COSY NMR prediction (6)
SYNTHESIS
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2-(1,3-ditiano-2-ilideno)-acetonitrila (1): Cristal branco. Rendimento: 75%, 165 mg, pf. 60-63 °C, lit1 60-62 °C;

1 H RMN (300 MHz, CDCl3) δ 2,23 (m, J 6,8, 2H, CH2); 3,01 (t, J 7,5, 2H, SCH2); 3,06 (t, J 6,9, 2H, SCH2), 5,39 (s, 1H, CH);

13C RMN (75 MHz, CDCl3) δ 22,9 (CH2), 28,7 (SCH2), 28,8 (SCH2), 90,4 (CHCN), 116,3 (CN), 163,8 (C=CS). 

WILL BE UPDATED WATCH OUT.....................
Departamento de Química, Instituto Militar de Engenharia, Praça General Tiburcio
Instituto Militar de Engenharia, Rio de Janeiro. BELOW
Entrada do antigo Instituto de Química da UFRGS, um prédio histórico
Equipe - Os módulos foram fabricados na Unisanta sob a supervisão do professor Luiz Renato Lia, coordenador do Curso de Engenharia Química, ...
Instituto de Florestas da Universidade Federal Rural do Rio de Janeiro
Praça General Tibúrcio
Praça General Tibúrcio com o Morro da Urca ao fundo
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.
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.
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.

Enzymatic resolution of antidepressant drug precursors in an undergraduate laboratory

 
EducaçãoQuim. Nova 2015, 38(2), 285-287

Enzymatic resolution of antidepressant drug precursors in an undergraduate laboratory

Luís M. R. SolanoI; Nuno M. T. LourençoII,*
This paper describes a multi-step chemo-enzymatic synthesis of antidepressant drug precursors.

http://dx.doi.org/10.5935/0100-4042.20140306

Publicado online: novembro 13, 2014
 
Quim. Nova, Vol. 38, No. 2, 285-287, 2015
 
Educação http://dx.doi.org/10.5935/0100-4042.20140306
 
*e-mail: nmtl@tecnico.ulisboa.pt
 
ENZYMATIC RESOLUTION OF ANTIDEPRESSANT DRUG PRECURSORS IN AN UNDERGRADUATE LABORATORY
 
Luís M. R. Solanoa and Nuno M. T. Lourençob,* a Faculdade de Farmácia da Universidade de Lisboa, Av. Prof. Gama Pinto, 1649-003 Lisboa, Portugal b Departamento de Bioengenharia, Instituto de Biotecnologia e Bioengenharia, Instituto Superior Técnico, Av. Rovisco Pais, 1, 1049-001 Lisboa, Portugal
 
Recebido em 07/07/2014; aceito em 17/09/2014; publicado na web em 13/11/2014
The use of biocatalysts in synthetic chemistry is a conventional methodology for preparing enantiomerically enriched compounds. Despite this fact, the number of experiments in chemical teaching laboratories that demonstrate the potential of enzymes in synthetic organic chemistry is limited. We describe a laboratory experiment in which students synthesized a chiral secondary alcohol that can be used in the preparation of antidepressant drugs. This experiment was conducted by individual students as part of a Drug Synthesis course held at the Pharmacy Faculty, Lisbon University. This laboratory experiment requires six laboratory periods, each lasting four hours. During the first four laboratory periods, students synthesized and characterized a racemic ester using nuclear magnetic resonance spectroscopy and gas chromatography. During the last two laboratory periods, they performed enzymatic hydrolysis resolution of the racemic ester using Candida antarctica lipase B to yield enantiomerically enriched secondary alcohol. Students successfully prepared the racemic ester with a 70%-81% overall yield in three steps. The enzymatic hydrolysis afforded (R)- secondary alcohol with good enantioselectivity (90%–95%) and reasonable yields (10%–19%). In these experiments, students were exposed to theoretical and practical concepts of aromatic acylation, ketone reduction, esterification, and enzymatic hydrolysis. Keywords: sec-alcohols; esters; lípase; enantiomers; resolution.
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Sunday, 22 March 2015

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Thursday, 12 March 2015

Odorless and Efficient Thioacetalization Reaction of Oximes





Chemical Journal of Chinese Universities  2012, Vol. 33 Issue (09): 1969-1972
DOI: 10.3969/j.issn.0251-0790.2012.09.016 http://www.cjcu.jlu.edu.cn/EN/abstract/abstract24471.shtml# http://www.cjcu.jlu.edu.cn/EN/volumn/next.shtml  
Odorless and Efficient Thioacetalization Reaction of Oximes    
YU Hai-Feng1, LIAO Pei-Qiu2
1. School of Chemistry and Life Science, Anshan Normal University, Anshan 114007, China;
2. Department of Chemistry, Northeast Normal University, Changchun 130024, China
Download: PDF (581 KB) Export: BibTeX | EndNote (RIS)      Supporting Info
Abstract  Thioacetals are important compounds because they can be considered as both useful protecting groups of carbonyl compounds in the synthesis of multi-functional complex molecules and acyl carbanion equi-valents in C—C bond forming reactions. Since many reactions have been developed to prepare oximes from non carbonyl compounds, to lead to a novel and efficient method for thioacetal preparation, transthioacetalization of oximes has received more and more attention. Unfortunately, the transformation usually suffers from the use of harmful, odorous thiols which can lead to serious safety and environment problems. From the green chemistry point of view, an efficient and odorless transthioacetalization of oximes involving an environment friendly reagent is of great importance and necessity. In this work, using odorless and stable α-oxo ketene dithioacetals 1 as thiol equivalents, the thioacetalization reaction of oximes 2 were studied. In the reaction system of MeCOCl-EtOH(95%) or 4-dodecylbenzenesulfonic acid(DBSA)-H2O, the thioacetalization reaction were carried out in reflux temperature. It is noteworthy that the odor of thiols can not be perceived during either the reaction or workup.
 Odorless and Efficient Thioacetalization Reaction of Oximes[J].
Chemical Journal of Chinese Universities, 2012, 33(09): 1969-1972.
URL:
http://www.cjcu.jlu.edu.cn/EN/10.3969/j.issn.0251-0790.2012.09.016     OR
  http://www.cjcu.jlu.edu.cn/EN/Y2012/V33/I09/1969
  Odorless and Efficient Thioacetalization Reaction of Oximes.pdf (1)


  Odorless and Efficient Thioacetalization Reaction of Oximes.pdf (2)


Anshan Normal University, Anshan 114007, China















Department of Chemistry, Northeast Normal University, Changchun 130024, China - See more at: http://organicsynthesisinternational.blogspot.in/#sthash.dl5jq4SB.dpuf











Friday, 6 March 2015

7-allyl-6-hydroxy-indan-1-one...Mom will teach you NMR

Figure US08242291-20120814-C00009


Thermal Claisen rearrangement on 6-allyloxy-indan-1-one,  (III) to obtain 7-allyl-6-hydroxy-indan-1-one, (IV):
  • Formula: C12H12O2
  • Molecular Weight: 188.22200
Synonyms:



http://www.google.com/patents/US8242291
EXAMPLE 2
This example refers to reaction b of the process of the invention.
20 kg of the intermediate of formula (III) prepared as described in example 1 are suspended in 50 l of Dowtherm A under nitrogen flow. In an inert atmosphere, it is heated to approximately 200° C. for approximately 5 hours. Upon completion of the reaction (TLC) a clear red-brown solution is obtained, without the formation of black pitch. The reaction mixture is cooled slowly to 25° C. (a partial precipitation is observed). 100 l (5 volumes) of cyclohexane are added and it is cooled to between 0 and 5° C. for one hour. It is filtered by washing with cyclohexane and dried at reduced pressure and T=45° C. for at least 12 hours. 16.8 kg of yellow solid are obtained which is refluxed in 80 l of toluene in the presence of decolouring carbon. The suspension is filtered, washing it with hot toluene. Part of the solvent is distilled at reduced pressure until the beginning of crystallisation. It is cooled at room temperature and then to between 0 and 5° C. for at least one hour.
The filtered solid is washed with cold toluene and dried at reduced pressure at T=45° C. for at least 12 hours. 15.3 kg of intermediate (IV) are obtained in the form of an almost white solid of quality suitable for continuation of the synthesis.
1H-NMR and mass spectroscopic analyses are performed on part of the product thus obtained, purified by chromatography for analytical purposes (silica gel, 7 parts in volume of heptane—3 parts in volume of ethyl acetate), obtaining the following results:
Electron impact mass: [M+]=188
1H-NMR (500 MHz, CDCl3): δ (ppm)
2.72 ppm, t, J=6 Hz, 2H,  AR C=OCH2 CH2 AR
3.03 ppm, t, J=6 Hz, 2H, AR C=OCH2 CH2 AR
4.03 ppm, d, J=6 Hz, 2H, ARCH2CH=CH2
5.13-5.20, Σd, 2H, ARCH2CH=CH2
5.60 ppm, s, 1H, 0H
5.98-6.10 ppm, m, 1H, CH2CH=CH2
7.13 ppm, d, J=8 Hz, 1H, AR
7.25, d, J=8 Hz, 1H. AR

PREDICT
1H NMR

CLICK ON PICTURE

6-hydroxy-7-prop-2-enyl-2,3-dihydroinden-1-one NMR spectra analysis, Chemical CAS NO. 320574-77-4 NMR spectral analysis, 6-hydroxy-7-prop-2-enyl-2,3-dihydroinden-1-one H-NMR spectrum




13 C NMR

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6-hydroxy-7-prop-2-enyl-2,3-dihydroinden-1-one NMR spectra analysis, Chemical CAS NO. 320574-77-4 NMR spectral analysis, 6-hydroxy-7-prop-2-enyl-2,3-dihydroinden-1-one C-NMR spectrum

6-hydroxy-7-prop-2-enyl-2,3-dihydroinden-1-one

COSY PREDICT


HMBC PREDICT

................ 
COCK SAYS MOM CAN TEACH YOU NMR


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Khajuraho Group of Monuments is located in India
Khajuraho Group of Monuments
Location of Khajuraho Group of Monuments in India.

Location in Madhya PradeshLocation in Madhya Pradesh

  1. 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, ...























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