Cleavage of the Methylenedioxy Ring in the Grignard Reaction of 3,4-Methylenedioxybenzonitrile

1974 ◽  
Vol 52 (22) ◽  
pp. 3784-3786 ◽  
Author(s):  
Janet E. Forrest ◽  
Ronald A. Heacock ◽  
Thomas P. Forrest
Keyword(s):  
Spectroscopic Properties ◽  
Magnesium Bromide ◽  
Grignard Reaction ◽  
Ethyl Magnesium Bromide

The reaction of 3,4-methylenedioxybenzonitrile (2) with ethyl magnesium bromide gives products resulting from opening of the methylenedioxy ring, namely 4-hydroxy-3-n-propoxypropiophenone (3) and 3-hydroxy-4-n-propoxypropiophenone (4) in addition to the expected product 3,4-methylenedioxypropiophenone (1). The isomeric hydroxy-n-propoxy ketones were differentiated on the basis of their spectroscopic properties.

Structural preferences for the double bond position in some unsaturated 3,3-diphenylpyrrolidines

1970 ◽  
Vol 48 (23) ◽  
pp. 3742-3745 ◽  
Author(s):  
M. M. A. Hassan ◽  
A. F. Casy
Keyword(s):  
Double Bond ◽  
Methyl Iodide ◽  
Quaternary Salt ◽  
Double Bond Position ◽  
Magnesium Bromide ◽  
Free Base ◽  
Spectroscopic Evidence ◽  
Structural Preferences ◽  
Ethyl Magnesium Bromide ◽  
Sole Product

The reaction between 3,3-diphenyl-3-cyano-1-methylpropyl isocyanate and ethyl magnesium bromide leads to 2-ethyl-5-methyl-3,3-diphenyl-1-pyrroline rather than the isomeric 2-ethylidenepyrrolidine. The protonated N-methyl analogue (identical with a major metabolite of methadone) retains the 1-pyrroline structure, but the free base is a cis-trans mixture of the corresponding 2-ethylidenepyrrolidines; the cis Me/Ph isomer preponderates and is the sole product (obtained as a quaternary salt) when the mixture is treated with methyl iodide. 5-Methyl-2-methylene-3,3-diphenylpyrrolidine, a lower homologue of the methadone metabolite, isomerizes to a 1-pyrroline derivative when protonated or methylated. All structural conclusions are based on i.r. and p.m.r. spectroscopic evidence.

Grignard Reaction of 2-Substituted-3-Cyanoquinolines

1985 ◽  
Vol 40 (7) ◽  
pp. 990-995 ◽  
Author(s):  
◽  
Balkrishen Bhat ◽  
A. P. Bhaduri
Keyword(s):  
Cyano Group ◽  
The Other ◽  
Magnesium Bromide ◽  
Grignard Reaction ◽  
Reaction Products ◽  
Grignard Reactions ◽  
Magnesium Halide ◽  
Activated Surface

Abstract Grignard reactions of 2-morpholino and 2-methylthio-3-cyanoquinoline, 2-chloro-3-cyanoquinoline, 2-chloro-3-cyano-6-methoxyquinoline and 2-chloro-3-cyano-7-methylquinoline with alkyl or aryl magnesium halides have been studied. It was found that 2-morpholino and 2-methylthio- 3-cyanoquinolines gave 1,4-addition products followed by rapid aromatisation. 2-Chloro-3- cyanoquinoline with alkyl magnesium halides furnished 1,4-addition products but with aryl magnesium halides 1,4- and 1,2-addition products were obtained. The cyano group of 4-aryl-2-chloro- 3-cyano-1,4-dihydroquinolines was found to participate in the Grignard reaction to yield 1,2- addition products. 2-Chloro-3-cyano-6-m ethoxyquinoline with alkyl and phenyl magnesium halides yielded exclusively 1,4-addition products. Similarly with p-m ethoxyphenyl magnesium bromide, 1,4-addition products were isolated which participated in the Grignard reaction to yield the expected adducts. Unlike the other chloroquinoline derivatives, 2-chloro-3-cyano-7-methylquinoline with alkyl magnesium halide formed 1 ,2-addition products but with aryl magnesium halides, 1,4-addition products were isolated. The 4-alkyl-2-chloro-3-cyano-l,4-dihydroquinolines were unstable as compared to their 4-aryl analogs. A couple of the Grignard reaction products were found to be unstable on activated surface.

Some piperazino analogues of methadone and related ketones: a novel conversion of an N-carbethoxy to a triethylmethyl group

1969 ◽  
Vol 47 (13) ◽  
pp. 2413-2419
Author(s):  
J. R. Dimmock ◽  
N. J. Harper ◽  
R. Islam ◽  
A. F. Casy
Keyword(s):  
Cyano Group ◽  
Magnesium Bromide ◽  
Dimethylamino Group ◽  
Ethyl Magnesium Bromide ◽  
Derivatives Of ◽  
Related Compounds

A number of derivatives of methadone and related compounds have been prepared, where the dimethylamino group has been replaced by a 4-substituted piperazino function. The preparation of these compounds involved the reaction of N-ω-cyanoalkyl-N′-carbethoxy piperazines with ethyl magnesium bromide, and various products were obtained. These included replacement of the N′-carbethoxy group by a triethylmethyl function and cleavage of the carbethoxy group. In some cases the ω-cyano group reacted to give the corresponding ketone. Reactions of 1-benzyl-4-carbethoxy piperazine with ethyl magnesium bromide and phenyl magnesium bromide gave no evidence for the formation of the triethylmethyl group. However, cleavage of the carbethoxy group occurred and there was evidence for the formation of the corresponding amide.

scholarly journals Preparation of Ethyl Magnesium Bromide for Regiospecific Analysis of Triacylglycerols

2008 ◽  
Vol 57 (8) ◽  
pp. 459-462 ◽  
Author(s):  
Yasuhiro Ando ◽  
Yuki Tomita ◽  
Yusuke Haba
Keyword(s):  
Magnesium Bromide ◽  
Regiospecific Analysis ◽  
Ethyl Magnesium Bromide

scholarly journals SINTESIS FEROMON 6-METIL-2-HEPTEN-4-OL DARI KROTONALDEHID MELALUI PEMBENTUKAN REAGEN GRIGNARD ISOBUTILMAGNESIUM BROMIDA

2010 ◽  
Vol 5 (2) ◽  
Author(s):  
Putu Indrayani ◽  
Aliefman Hakim
Keyword(s):  
Grignard Reagent ◽  
Refraction Index ◽  
Magnesium Bromide ◽  
Grignard Reaction ◽  
Stretching Vibration ◽  
Nh4cl Solution

Abstrak : Sintesis 6-metil-2-hepten-4-ol diawali dengan pembentukan reagen Grignard isobutilmagnesium bromida pada 400C selama 1 jam, dilanjutkan dengan pembentukan garam alkoksi magnesium bromida pada 00C.Hidrolisis terhadap garam alkoksi magnesium bromida dengan larutan NH4Cl jenuh menghasilkan 6-metil-2-hepten-4-ol. Hasil sintesis kemudian diuji sifat fisiko-kimianya meliputi berat jenis, indeks bias serta identifikasi denganSpektrofotometer Inframerah (IR), Kromatografi Gas (GC) dan Kromatografi Gas-Spektrometer Massa (GC-MS). Hasil sintesis menghasilkan cairan beraroma manis segar, berwarna kekuningan, berat jenis 0,81529 g/mL, indeks bias 1,40830, kemurnian 66,07 % dan hasil 46,31 %. Karakter IR senyawa hasil sintesis menunjukkan vibrasi ulur O-H alkohol pada 3361 cm-1, vibrasi ulur C-OH pada 1049,2 cm-1, vibrasi ulur C=C pada 1676 cm-1 dan serapan 2956,7 dan 2920 cm-1 untuk vibrasi ulur C-H dalam CH 3 dan spektra massa dengan m/e 128 yang dicapai pada waktu retensi 6,284 menit. Data-data tersebut mendukung bahwa senyawa hasil sintesis adalah 6-metil-2-hepten-4-ol.Kata kunci : Sintesis, reaksi Grignard dan 6-metil-2-hepten-4-olAbstract : Synthesis of 6-methyl-2-hepten-4-ol was generated with formation of Grignard reagent Isobutylmagnesium bromide carried out at 400C for one hour, then formation of alcoxide salt magnesium bromide carried out at 00C. Alcoxide salt magnesium bromide were hydrolyzed by saturated NH4Cl solution producing 6-methyl-2-hepten-4-ol. Results were examined physically and chemically including density, refraction index, pure percentage and yield percentage were 0,81529 g/mL, 1,40830, 66,07 % and 46,31 % respectively. The IR characters showed stretching vibration of O-H group at 3361 cm-1, stretching vibration C-OH group at 1049,2 cm-1, stretching vibration C=C group at 1676 cm-1 and absorption of C-H in CH3 2956,7 and 2920 cm-1. Identification using GC-MS resulted spectra m/e 128 at time retention 6,284 minutes. The proven data indicated that the resulted compound was 6-methyl-2-hepten-4-ol.Keywords : synthesis, Grignard reaction and 6-methyl-2-hepten-4-ol

scholarly journals THE ACTION OF ETHYL MAGNESIUM BROMIDE ON ANTHRAQUINONE.1

1911 ◽  
Vol 33 (12) ◽  
pp. 1966-1973
Author(s):  
Latham Clarke ◽  
Paul Whittier Carleton
Keyword(s):  
Magnesium Bromide ◽  
Ethyl Magnesium Bromide
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