Preparation of Functionalized Arylmagnesium Reagents Bearing ano-Chloromethyl Group

2000 ◽  
Vol 65 (23) ◽  
pp. 8108-8110 ◽  
Author(s):  
Thomas Delacroix ◽  
Laurent Bérillon ◽  
Gérard Cahiez ◽  
Paul Knochel
Keyword(s):  
Chloromethyl Group

scholarly journals UNUSUAL WAY OF REACTION OF 3-AMINO-4-(5-CHLOROMETHYL-1,2,4-OXADIAZOLE-3-YL)-FURAZAN WITH HYDRAZINE

2017 ◽  
Vol 60 (4) ◽  
pp. 26
Author(s):  
Elena V. Stepanova ◽  
Andrei I. Stepanov
Keyword(s):  
Carboxylic Acid ◽  
Catalytic Amount ◽  
Acid Synthesis ◽  
Chloromethyl Group ◽  
One Pot ◽  
Isolation And Purification ◽  
Long Duration ◽  
Reaction Proceeds ◽  
Selective Reactivity ◽  
Hydrolysis Of

The results of our study of the pathways of selective reactivity of 3-amino-4-(5-chloromethyl-1,2,4-oxadiazole-3-yl)furazan versus 5-unsubstituted or 5-methyl and 5-trifluoromethyl substituted 4-(5R-1,2,4-oxadiazole-3-yl)furazans (R = H, Me, CF3) towards the action of hydrazine are discussed. If the reductive opening of 1,2,4-oxadiazole ring in unsubstituted at the С-5 atom (1,2,4-oxadiazol-3-yl)furazan derivatives under the treatment with hydrazine can be used as a method for the preparation of a range of amidrazones of 4-R-furazan-3-carboxylic acid. 3-amino-4-(5-trifluoromethyl-1,2,4-oxadiazol-3-yl)furazan with hydrazine gives amidoxime of 4-aminofurazan-3-carboxylic acid. 3-amino-4-(5-methyl-1,2,4-oxadiazol-3-yl) furazan is inert to the action of hydrazine, on the contrary the reaction of 3-amino-4-(5-chloromethyl-1,2,4-oxadiazole-3-yl)furazan with hydrazine leads to oxidation of chloromethyl group of titled compound to the carbonyl one. In this case the product of reaction of 3-amino-4-(5-chloromethyl-1,2,4-oxadiazole-3-yl)furazan with hydrazine was isolated in a form of corresponding hydrazonomethyl derivative notably as 3-amino-4-(5-hydrazonomethyl-1,2,4-oxadiazole-3-yl)furazan. A possible reaction mechanism for the formation of hydrazonomethyl group by oxidation reaction of chloromethyl group by hydrazine is proposed. 3-Amino-4-(5-hydrazonomethyl-1,2,4-oxadiazol-3-yl)furazan undergoes a transhydrazination reaction with semicarbazide and thiosemicarbazide. But our attempts to its hydrolysis for the purpose to obtain free aldehyde were unsuccessful. Thus, hydrolysis of hydrazonomethyl derivative in acetic acid in the presence of catalytic amount of sulfuric acid results in azine – N,N'-bis(3-(4-aminofurazan-3-yl)-1,2,4-oxadiazol-5-ylmethylyden)hydrazine – precipitation, long-duration boiling in hydrochloric acid leads to Kishner-Wolff reduction of the carbonyl group to 3-amino-4-(5-methyl-1,2,4-oxadiazol-3-yl)furazan, and hydrolysis in alkaline medium leads to 1,2,4-oxadiazole ring opening to amidoxime of 4-aminofurazan-3-carboxylic acid. Synthesis of 3-amino-4-(5-chloromethyl-1,2,4-oxadiazole-3-yl)furazan (R = CH2Cl) was carried out by condensation of amidoxime of 4-aminofurazan-3-carboxylic acid with an excess of chloroacetyl chloride in toluene at elevated temperature. The reaction proceeds through formation of intermediate product – 3-chloromethylamino-4-(5-chloromethyl-1,2,4-oxadiazol-3-yl)furazan. Removing of N-chloroacetyl group in such obtained intermediate was performed by hydrolysis in acidic media. One-pot synthesis without the need for isolation and purification of intermediate is allowed. The structures of obtained compounds were proved by modern methods of physical-chemical analysis (1H, 13C NMR, IR and MS spectroscopy).Forcitation:Stepanova E.V., Stepanov A.I. Unusual way of reaction of 3-amino-4-(5-chloromethyl-1,2,4-oxadiazole-3-yl)furazan with hydrazine. Izv. Vyssh. Uchebn. Zaved. Khim. Khim. Tekhnol. 2017. V. 60. N 4. P. 26-32.      

A Raman Spectroscopy Study of the Chloromethyl Group Attached to an Aliphatic Hydrocarbon Chain

1973 ◽  
Vol 27 (1) ◽  
pp. 27-30 ◽  
Author(s):  
T. S. Wang ◽  
J. J. Mannion
Keyword(s):  
Raman Spectroscopy ◽  
Hydrogen Atom ◽  
Carbon Atom ◽  
Chlorine Atom ◽  
Hydrocarbon Chain ◽  
Aliphatic Hydrocarbon ◽  
Rotational Isomer ◽  
Spectroscopy Study ◽  
Chloromethyl Group ◽  
Infrared Studies

The chloromethyl group (—CH2Cl) attached to a normal hydrocarbon chain gives rise to two characteristic Raman bands near 660 and 730 cm−1. The band at 660 cm−1, which is very intense, is assigned to a stretching mode of the C-Cl linkage when the chlorine atom is trans to a hydrogen atom. The less intense peak at 730 cm−1 is assigned to the same mode of the rotational isomer with the chlorine atom trans to a carbon atom. These assignments are consistent with those reported in infrared studies. In contrast to almost equal intensities for both bands in the infrared, the band at 660 cm−1 proved to be the strongest by far in Raman spectra.

ChemInform Abstract: Preparation of Functionalized Arylmagnesium Reagents Bearing an o-Chloromethyl Group.

ChemInform ◽  
2001 ◽  
Vol 32 (14) ◽  
pp. no-no
Author(s):  
Thomas Delacroix ◽  
Laurent Berillon ◽  
Gerard Cahiez ◽  
Paul Knochel
Keyword(s):  
Chloromethyl Group

New Dibenzocyclooctadiene Lignans from Schisandra sphenanthera and Their Proinflammatory Cytokine Inhibitory Activities

2010 ◽  
Vol 65 (2) ◽  
pp. 1-8 ◽  
Author(s):  
Rong Ren ◽  
Xin-Xin Ci ◽  
Hai-Zhou Li ◽  
Guo-Jun Luo ◽  
Rong-Tao Li ◽  
...  
Keyword(s):  
Higher Plants ◽  
2D Nmr ◽  
Spectroscopic Techniques ◽  
Chloromethyl Group ◽  
Cellular Toxicity ◽  
Schisandra Sphenanthera ◽  
Tnf Α ◽  
2D Nmr Spectra ◽  
Factor Α ◽  
Necrosis Factor

Investigation of the fruits of Schisandra sphenanthera led to the isolation of two new dibenzocyclooctadiene lignans, methylgomisin O (1) and chloromethyl schisantherin B (2), together with twelve known lignans (3 - 14). Their structures were elucidated by using extensive spectroscopic techniques including 1D and 2D NMR spectra. Compound 2 was identified as a cyclooctadiene moiety substituted with a chloromethyl group, which is rarely found in natural products, especially in terrestrial higher plants. Among these isolates, compounds 1 and 7 exhibited considerable inhibitory activity against tumor necrosis factor-α (TNF-α) and interleukin-6 (IL-6) production, and did not display any cellular toxicity against RAW264.7 cells.

SOME DERIVATIVES OF DIALKOXY-PHTHALIDES

1944 ◽  
Vol 22b (4) ◽  
pp. 115-124 ◽  
Author(s):  
Richard H. F. Manske ◽  
Archie E. Ledingham
Keyword(s):  
Benzoic Acids ◽  
Chloromethyl Group ◽  
Fries Rearrangement ◽  
Derivatives Of

Treatment of certain dialkoxy-benzoic acids was found to yield dialkoxy-phthalides containing a chloromethyl group. The constitutions of a number of these compounds have been elucidated by unambiguous syntheses. Inter alia, it was observed that the Fries rearrangement of 4-acetoxy-3-methoxy-toluene yielded exclusively a m-hydroxy-acetophenone. This appears to be the only recorded case of an exclusive meta-rearrangement. Several intermediate aldehydes and some compounds derived from them are described.

Synthesis and Properties of Linear Chloroacetylated Polystyrene

2010 ◽  
Vol 428-429 ◽  
pp. 102-105
Author(s):  
Hong Chi Zhao ◽  
Juan Li Guo ◽  
Ai Juan Sun ◽  
Ling Ling Gao
Keyword(s):  
Aluminium Chloride ◽  
Chloroacetyl Chloride ◽  
Cross Link ◽  
Reaction Conditions ◽  
Chloromethyl Group ◽  
Reaction Method ◽  
Anhydrous Aluminium Chloride ◽  
Optimum Reaction ◽  
Thermal Stability Of ◽  
Carcinogenic Compound

Polystyrene (PS) was synthesized by emulsion polymerization. The linear chloroacetylated PS was prepared high effectively by Friedel-Crafts acetylation of PS using chloroacetyl chloride and anhydrous aluminium chloride as chloroacetylation reagent and catalysts, respectively. The structure of chloroacetyl group is similar to that of chloromethyl group. In this method, carcinogenic compound (chloromethyl ether etc.) was avoided and the reactions of secondary cross link and multi-substitute could be eliminated. The resultant polymers were characterized by Fourier transform infrared spectrometery (FTIR) and thermogravimetric analysis. The effects of reaction conditions on chloroacetylation were studied, and the optimum reaction conditions were obtained. Chloroacetyl group was introduced into benzene ring of PS because of the appearance of the absorption peaks at 1695cm-1 (due to C=O bonds) and 644cm-1 (due to C-Cl bonds) in the FTIR spectrum. The thermal stability of the chloroacetylated PS was decreased with increasing chloroacetyl group. Moreover, there were two decomposing stages. The glass transition temperature of chloroacetylated PS increased with substitution value increasing. The effects of the reaction conditions such as reaction temperature, the solvent amount and the concentration of chloroacetyl chloride and anhydrous aluminium chloride on the chloroacetylation of PS were obvious. The certain loading can be controlled when it is lower than the maximum loading of chloroacetylated PS. The reaction condition is gentle and the operation is safe, simple and economical so that Friedel-Crafts acetylation of PS is an ideal reaction method.

scholarly journals NMR spectroscopic properties of furo[2′,3′:4,5]pyrrolo[1,2-d][1,2,4]triazine derivatives

2017 ◽  
Vol 16 (2) ◽  
pp. 147-151 ◽  
Author(s):  
Ivana Zemanová ◽  
Renata Gašparová
Keyword(s):  
Chemical Shift ◽  
Carbonyl Group ◽  
Chemical Shifts ◽  
Spectroscopic Properties ◽  
Chloromethyl Group ◽  
Nmr Chemical Shifts ◽  
H Nmr ◽  
Triazine Derivatives ◽  
C Nmr ◽  
Electron Withdrawing Substituents

Abstract The 1H and 13C NMR spectroscopic properties of a series of furo[2′,3′:4,5]pyrrolo[1,2-d][1,2,4]triazin-8(7H)-ones and -thiones were investigated. The influence of various electron donating as well as electron withdrawing substituents at C-5 or N-7 on 1H NMR chemical shifts as well as 13C chemical shifts at C8 were observed. The 5-chloromethyl group had a little influence on the chemical shift of H-7 proton and the 8-thione group causes deshielding of H-7 as well as H-5 protons in comparison with the C-8 carbonyl group.

MNDO conformations of chloromethyloxirane and solvent effect

1982 ◽  
Vol 47 (12) ◽  
pp. 3199-3205 ◽  
Author(s):  
Igor Tvaroška
Keyword(s):  
Experimental Data ◽  
Solvation Energy ◽  
Point Of View ◽  
Molecular Characteristics ◽  
Single Bond ◽  
Chloromethyl Group ◽  
The Third ◽  
Gauche Effect ◽  
The Individual ◽  
Semi Empirical

Structure of chloromethyloxirane during rotation around the C-C single bond connecting oxirane ring and chloromethyl group has been studied theoretically in twelve solvents. Molecular characteristics and energy of the isolated molecule have been calculated by the semi-empirical MNDO method of molecular orbitals. The MNDO calculation predicts the existence of only two synclinal conformers G-1 and G-2, more stable being the less polar G-2, μ = 2.39 . 10-30 mC. However, the calculation carried out for dilute solutions including the solvation energy by the method of continuum reveals the presence of the third, antiperiplanar conformer T, μ = 9.26 . 10-30 mC. Populations of the individual conformers depend considerably on solvent, the most stable in ethanol being G-1, μ = 11.06 . 10-30 mC. The results obtained are compared with experimental data and also discussed from the point of view of the gauche effect.

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