EA039261B1 - METHOD FOR PRODUCTION OF 1,2-N,N'-BIS-AMINOTETRAMETHYL-1,2-n,n'-DICHLORODIPHENYLETHYLENE - Google Patents

Abstract

The invention relates to new compounds, in particular to a method for the production of a new organic compound 1,2-N,N'-bis-animotetramethyl-1,2-n,n'-dichlorodiphenylethylene (1). The objective of the invention is the production of a new organic compound with a specific structure using a simple method in order to complement the general catalog of organic compounds and reagents. The method for the production of 1,2-N,N'-bis-animotetramethyl-1,2-n,n'-dichlorodiphenylethylene includes the interaction of two components under acceptable conditions. NaOH solution (pH 12) is added to the mixture of chlorobenzene and dimethylformamide. The reaction mass is mixed for 7 h at 70C; during mixing, it is observed that the solution color changes towards yellow coloring, and pH of the solution declines down to neutral condition. At the end of reaction, the reaction medium splits and separates into two layers. The bottom layer is separated, evaporated in a vacuum until stable crystals are formed; then these crystals are washed with cold methanol and recrystallized from hot methanol. The product is separated using filtering and dried in a vacuum. Using chromatographic analysis methods (paper chromatography, thin-layer chromatography, high performance liquid chromatography), the purity of derived product was determined, and it was detected that the compound (1) consists of two geometric cis and trans isomers: The output of cis and trans isomers is 55.06% and 44.94% with melt. temp. 225-227C and 250-252C, respectively. The compound (1) is highly soluble in water.

Description

Distinctive features of the formation of 1,2-N,N'-bis-aminotetramethyl-1,2-n,n'-dichlorodiphenylethylene are that the reaction proceeds according to a special mechanism, which includes the formation of two intermediate transition ionic compounds: 1, 2-N,N'-bis-aminotetra sodium methylethylenedioxyionate (A) and sodium-1,2-N,N'-bis-aminotetramethylethylenediol (B), and then with the transition to a stable compound (1).

The aim of the invention is a simple way to obtain a new organic compound (1) with a specific structure, complementing the general catalog of organic compounds and reagents.

The preparation of compound (1) by reacting chlorobenzene with dimethylformamide in an alkaline medium (NaOH) by stirring for 7 hours at 70°C is described. With stirring, a change in the color of the solution towards yellow coloration and a decrease in the pH of the solution to a neutral state are observed. At the end of the reaction, the reaction medium separates and separates into two layers. The lower layer is separated, evaporated in vacuum until stable crystals are formed, which are filtered, washed and purified from impurities with cold methanol. The resulting product (1) contains two geometric isomers: cis- and trans- with different yields and melting points. The product is highly soluble in water.

A compound with a similar structure may have stereochemical features and configurational stability, as well as biological activity. The advantages of the proposed method are:

availability of reagents;

carrying out the synthesis in a safe environment and the absence of the use of flammable liquids;

increasing the yield of the product due to the synthesis and proportion of the reactants.

The structure of the resulting compound (1) was confirmed by UV, IR, 1H NMR, ¹³ C NMR, mass spectrometry, and elemental analyses. In FIG. 1 shows the UV spectra of this substance. The absorption band in the region of 194-210 nm (weak) refers to the >C=C< bond. The absorption band at 218 nm (Lge2.64) refers to C=C-C6H4C1, the absorption at 294 nm refers to the C6H4Cl group, the absorption at 374 nm N (free electron pair of amine nitrogen). The spectrum in the region of 249 and 254 (Lge 0.108-0.109) nm refers to benzene nuclei in cis- and trans-positions. The mass spectrum (Fig. 2) of this ^compound contains intense m/z ^{fragments : +} , 227[M-(CH3CH32a)] ⁺ , 209[M-(CH3CH ₃ CH ₃ 2a)] ⁺ , 195[M-((CH3 )42Cl)] ⁺ , 140[M-((CN)2(CH ₃ ) ₄ 2Cl)] ⁺ .

The 1H NMR spectrum (6 ^ppm ) (Fig. 3) contains signals related to proton absorption at: in ClC=CH), 8.01, 8.06, 8.12, 8.34 (4H, s).

In NMR ¹³ С ppm (Fig. 4) observed chemical shifts of nuclei in the following areas: ar. C-Cl (151); C ₂ , C ₃ , C ₅ , C ₆ (170.91, 171.37, 171.44, 171.87).

The IR spectra (cm ^-1 ) (Fig. 5) of the obtained product have the corresponding absorption bands: 1384 (CH ₃ ), 1654, 1649, 1635 (C=C), 3088, 792, 775 (ar.) 1066, 1047 (ar.C-Cl). The absorption bands at 1654 and 1649 cm ^-1 refer to the cis and trans isomers of this compound (1).

Elemental analysis of the product shows the following ratios of elements, %: C=64.76, H=5.66, N=8.51.

Calculated values for the gross formula C, H, N, %: C=64.47, H=5.97, N=8.35.

Chromatographic analysis was carried out on chromatographic plates Silifol (Czech Republic) and DRieselgel 60 (Merk) Germany in the system HCOOH:CH ₃ COOH:H ₂ O:CH ₃ OH (150:50:300:500) (A), (C ₂ H ₅ ) ₃ N:NH ₄ OH:CH ₃ OH:H ₂ O (10:10:200:400) (B), CH ₃ COOH:pyridine:ethyl acetate (125:25:20) (C).

Developers: solutions of nihydrin and iodine vapor. IR spectra were taken on a SHIMADRUFTIR instrument

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measure. Mass spectra were taken on a MALDI-TOF instrument. 1H NMR spectrum was obtained on a Bruker AM-300 spectrophotometer (75.5 and 300 MHz, respectively) in CDCl ₃ internal standard SiMe4. Elemental analysis was performed on a Variomicro CHNS instrument.

HPLC was used to chromatographically separate the cis and trans isomers of 1,2-N,N'bis-aminotetramethyl-1,2-n,n'-dichlorodiphenylethylene (FIG. 6). The use of a system of solvents from CF3COOH and water makes it possible to carry out a fast (less than 6 min) and efficient separation of the studied mixtures of substances into the cis-isomer with a yield of 55.06%, with mp. 225-227°C and the trans isomer with a yield of 44.94%, m.p. 250-252°C.

The essence of the invention is illustrated by the following examples.

Example.

To a mixture of 10 ml (11 g) 0.0975 mol chlorobenzene, 10 ml (9.48 g) 0.13 mol dimethylformamide, add 15 ml 0.6 N NaOH (pH 12). The reaction mass is stirred for 7 hours at 70°C, during stirring, a change in the color of the solution towards yellow coloration and a decrease in the pH of the solution to a neutral state are observed. At the end of the reaction, the reaction medium separates and separates into two layers. The lower layer is separated, evaporated in vacuum until stable crystals form. The product obtained is washed with cold methanol, recrystallized, 7.630 g of chromatographically pure compound (1) is obtained from hot methanol with a yield of 70.32%. Rf1=0.85, developer iodine (A), Rf ₂ =8.08, iodine (B), Rf3=0.71 iodine (C).

Separation of compound (1) by HPLC led to the isolation of two geometric cis and trans isomers:

(n) C1 H ₄ C ₆ s ₆ H ₄ C1(n') C = C (CH ₃ ) ₂ cis isomer comp.(1)

trans-isomer comp.(1)

The cis isomer is obtained in 55.06% yield, m.p. 225-227°C, and the trans isomer is obtained with a yield of 44.94%, so pl. 250-252°C, respectively. The resulting product (1) is highly soluble in water. Qualitative reaction to a double bond:

1) pour a few ml of a solution of potassium permanganate (1%) into a test tube, add a few drops of sulfuric acid (conc.) and 3-4 ml of an aqueous solution of the obtained compound (1). Upon shaking, a discoloration of the solution occurs, confirming the presence of a double bond;

2) 2 ml of an aqueous solution of the product (1) is poured into a test tube and bromine water is added dropwise. Discoloration of bromine occurs, indicating the presence of a double bond;

3) qualitative reaction to the presence of chloride ions. 5 ml of an aqueous solution of the product (1) and 1 ml of a solution (4%) of silver nitrate are poured into a test tube, a white precipitate of silver chloride immediately precipitates, and upon standing, the precipitate turns black.

Claims (1)

The method of obtaining 1,2-N,N'-bis-aminotetramethyl-1,2-n,n'-dichlorodiphenylethylene by the interaction of dimethylformamide and chlorobenzene in an alkaline medium (NaOH) by heating at 70°C for 7 h, while the reaction the medium is stratified and separated into two layers, then the lower layer is separated, evaporated in vacuum until stable crystals form, which are filtered, washed with cold methanol and recrystallized from hot methanol.