SU677659A3 - Method of producing 2,4-dimethyl-3-carboxanylidfuran - Google Patents

Description

toluene, xylene, acetone, methyl ethyl ketone, ether, dioxane, acetonitrle, dichloroethane.

Example 1. Obtaining 2,4-dimethyl-3 (3-methoxycarboxanilide) furan.

23.1 g (0.1 mol) of 2,4-dimethyl-3- (3-hydroxycarboxanilide) -furan are added to 300 ml of anhydrous ethanol containing 3.9 g (0.1 mol) of potassium metal, and the mixture is stirred at room temperature for 4 hours. 14.1 g (0.1 mol) of methyl iodide is added to the solution, and the mixture is stirred at 40 ° C for 6 hours. After distilling off the ethanol and by-products, the remaining product is dissolved in 200 ml of benzene and washed with dilute aqueous sodium hydroxide and water saturated with sodium chloride. The product was dried with anhydrous sodium sulfate, the benzene was distilled off, and the product was recrystallized from a mixture of benzene and n-hexane (1: 2), to obtain 24.2 g of white flocculent crystals with a melting point. 120-123 ° C; the yield is 99.0%.

PRI me R 2.

Preparation of 2,4-dimethyl-3- (3-n-propyloxycarboxanilide) furan.

23.1 g (0.01 mol) of 2,4-dimethyl-3- (3-hydroxycarboxanilide) furan is dissolved in 300 ml of methanol, containing 2.3 g (0.1 mol) of metallic sodium, and the mixture stirred at room temperature for 3 hours, then 12.3 g (0.1 mol) of propyl bromide was added dropwise to the solution. After the addition is complete, the mixture is heated by refluxing for 6 hours. After the completion of the reaction, the mixture is poured into ice water, the precipitated crystals are filtered, dried and recrystallized from methanol, 10.4 g of light yellow needles are obtained with a m.p. 117-118 ° C; yield 74.5%.

Example 3. Obtaining 2,4-dimethyl-3 (3-isopropyloxycarboxanilide) furan.

23.1 g (0.1 mol) of 2,4-dimethyl-3- (3-hydroxycarboxanilide) furan was added to 200 ml of 0.5N. a solution of sodium hydroxide in water and the mixture is stirred for 2 hours. Then, 14.8 g (0.12 mol) of isopropyl bromide and 200 ml of methanol are added dropwise to the mixture while cooling with ice water. After the addition is complete, the mixture is heated to 60 ° C and stirred for 4 hours. After distilling off the methanol, the product is extracted with benzene and washed with water, the benzene is distilled off, the product is recrystallized from a mixture of methanol and water and 20.4 g of light brown crystals are obtained with m. square 80-82 ° C; yield 75.3%.

IR spectrum, cm (tablets): KBG VNH 3320 (S); vcH2875 (M); vco 1645 (s); 1620 (S).

Example 4. Obtaining 2,4-dimethyl-3 (2-ETHILOXY-5 - methylcarboxanilide) furan.

24.5 g (0.1 mol) of 2,4-dimethyl-3- (2-oxy-5methylcarboxanilide) furan is dissolved in

50 ml 2 n. an aqueous solution of potassium hydroxide, 100 ml of ethanol and 10.9 g (0.1 mol) of ethyl bromide are added to the solution. At the end of the addition, the mixture is heated at

50 ° C and stirred for 6 hours. Then the reaction mixture is poured into water, the precipitated crystals are filtered and recrystallized from a mixture of methanol and water, to obtain 23.8 g of white crystals with

m.p. yield 87.1%.

Example 5. Obtaining 2,4-dimethyl-3 (3-propargyloxycarboxanilide) furan.

23.1 g (0.1 mol) 2,4-dimethyl-3- (3-hydroxycarboxanilide) furan, 17.9 g (0.15 mol)

propargyl bromide and 10.0 g (0.1 mol) of sodium carbonate are added to 250 ml of acetone and the mixture is heated by reverse distillation with stirring for 8 hours. The reaction mixture is cooled and filtered,

The filtrate is evaporated and the remaining product is crystallized from a mixture of methanol and water, to obtain 24.9 g of white crystals with t. Il. 109-HS; yield 88.1%.

Example 6. Obtaining 2,4-dimethyl-3 (3-allyloxycarboxanilide) furan.

23.1 g (0.1 mol) of 2,4-dimethyl-3- (3-hydroxycarboxanilide) furan and 12.1 g (0.1 mol) of allyl bromide are added to 240 ml of anhydrous toluene. The mixture is cooled and stirred, 8.0 g (0.1 mol) of pyridine is added dropwise. At the end of the addition, the mixture was stirred at 30 ° C for 10 hours, while hydrobromide was isolated.

pyridine. The product is washed with a dilute aqueous solution of sodium hydroxide, water, and a saturated aqueous solution of sodium chloride. It is then dried with anhydrous sodium sulphate. The toluene was distilled off and the product was recrystallized from a mixture of methanol and water, 19.4 g of white crystals were obtained with a mp. 114-115 ° C; yield 73.2%.

IR spectrum, CM- (tablets) KBG: VNH 3280 (S); VCO 1650 (S); 1601 (S).

The compounds obtained according to the proposed method are given below:

2,4-dimethyl - 3- (2-methylcarboxanilide) furan; pink fibrous crystals, so pl. 130-132 ° C;

2,4 - dimethyl-3- (3-methylcarboxanilide) furan; light yellow crystals; m.p. 117.5-118.5 ° C;

2,4-dimethyl - 3- (4-methylcarboxanilide) furan; white needles; m.p.

127.5-128 ° C;

2,4 - dimethyl-3- (2,3 - dimethylcarboxanilide) -furan; light pink flake crystals; m.p. 156-158 ° C; 2,4 - dimethyl - 3- (2,4 - dimethylcarboxanilide) -furan; light yellow crystals; m.p. 108-112 ° C;

2,4-dimethyl-3- (2,5-dimethylcarboxanilide) furan; white powdery crystals; m.p. 144-147C;

2,4 - dimethyl - 3- (3,4-dimethylcarboxanilide) -furan; yellow .thin and white to yellowy. yl l; l-i il4 ° C .; .. ;;

2,4-dimethyl: -; ; 3- (3,5 - dimethyl zboxanilide) -furan; light yellow crystals; m.p. 149-152С ;; .; -; ,;

2,4-dimethyl-3- (2,4,6-trimethylcarbxanilide) furan; white needles; m.p. 174-175 ° C;

2,4-dimethyl - 3- (2-ethylcarboxanilide) furan; white powdered crystals; m.p. 108-HS; ..-

2,4 - dimethyl - 3- (2 - ox.icarboxanilide) furan; white flaky crystals; m.p. 170-17GS;

2,4-dimethyl - 3- (3-hydroxycarboxanilide) furan; white crystals; m.p. 147-148 ° C;

2,4 - dimethyl-3- (4 - oxycarboxanilide) furan; light pink crystals; m.p. 186-187 ° C;

2,4-dimethyl-3 - (2-methoxycarboxanilide) furan; white needles; m.p. 62-63 ° C .;

2,4 - dimethyl-3- (2-ethoxycarboxanilide) furan; light yellow needles; m.p. 71.5-73.5 ° C;

2,4-dimethyl - 3- (3 - methoxycarboxanilide) -furan; white flaky crystals; m.p. 120-123 ° C;

2,4 - dimethyl - 3- (4 - methoxycarboxanilide) -furan; white needles; m.p. 133-134 ° C;

2,4-dimethyl-3- (2,5-dimethoxycarboxanilide) furan; gray crystals, so pl. 90- 92 ° C;

2,4-dimethyl - 3- (2-methoxy-4-methylcarboxanilide) -furan; light brown crystals; m.p. 77.5-78.5 ° C;

2,4 - dimethyl-3- (2-ethoxy-methylcarboxanilide) -furan; white crystals; m.p. 79 ° C;

2,4-dimethyl - 3- (2-propoxy - 5-methylcarboxanilide) -furan; white powdery crystals; m.p. 62-63 ° C;

2,4 - dimethyl-3- (2 - "- propyloxycarboxanilide) -furan; white needles; m.p. 51-53 ° C;

2,4 - dimethyl - 3- (2-isopropyloxycarboxanilide) -furan; yellow, viscous liquid; m.p. 138-141 ° C / 0.008 mm Hg. v .; 1.5680;

2,4-dimethyl - 3- (2-n-butyloxycarboxyanilide) furan; white needles; m.p. 68.5-69 ° C;

2,4 - dimethyl-3- (2-allyloxycarboxanilide) -furan; white feather-like crystals; m.p. 59.0-59.5 ° C;

2,4-dimethyl - 3- (3-n-propyloxycarboxanilide) -furan; light yellow needles; m.p. 117-118 ° C;

2,4-dimethyl - 3- (3-isopropyloxycarboxanilide) -furan; light brown crystals; s; m.p. 80-82 ° C;

2,4 - dimethyl - 3- (3- "- butyloxycarboxanilide) -furan; light brown needles; m.p. 124-125 ° C;

2,4-dimethyl. - 3- (3 .-, "- hexyloxycarboxylic D) -furan; white needles; m.p. 122-123 ° C .; : .2,4 - dimethyl - 3- (3. - n-octyloxycarboxanilide) -furan; .. white, .instate; crystals; t: pl: -117-P9 ° C; ,: .: 2,4 - dimethyl-3- (3 - allyloxycarboxanyl) furan; white crystals; m.p. 114-115 ° C; , 2,4 - dimethyl-3- (3-propargyl-6-x-carboxanilide) furan; Belte crystals; T. PL, 109-PGS;

2,4-dimethyl .- 3- (2-chlorocarboxanilide) furan; light yellow needles; m.p. 108-109.5 ° C ;;

2,4 - dimethyl - 3- (3-chlorocarboxanilide) furan; light yellow powdered

crystals; m.p. 114-117 ° C;

2,4-dimethyl - 3- (4-chlorocarboxanilide) furan; white needles; m.p.

101 -103 ° C;

- 3- (4 - bromocarboxanilide) 2, 4-dimethyl furan; white needles; m.p. 159-160 ° C;

2,4 - dimethyl - 3- (2,4 - dichlorocarboxanilide) -furan; light yellow fine needles; m.p. 88.5-90 ° C;

2,4-dimethyl - 3- (2-methyl-3-chlorocarboxanilide) furan; white powdery crystals; m.p. 128-132 ° C;

2,4 - dimethyl-3- (2 - methyl-4 - chlorocarboxanilide) -furan; red-brown powdery crystals; m.p. 81.5-85 ° C;

2,4-dimethyl - 3- (2-trifluoromethylcarboxanilide) -furan; light yellow transparent

liquid; m.p. 102-110 ° C / 0.15 mm Hg v .;

2,4-dimethyl-3- (3-trifluoromethylcarboxanilide) -furan; yellow needles; m.p. 103.5-104.5 ° C;

2,4 - dimethyl-3- (2-chloro-5 - trifluoromethylcarboxanilide) -furan; white needles; m.p. 112-115 ° C;

2,4-dimethyl - 3- (4-cyanocarboxanilide) furan; brown needles; m.p. 140-142 ° C;

2,4-dimethyl-3- (4 - acetylcarboxanilide) furan; pale yellow needles; m.p. 146-147 ° C;

2,4-dimethyl - 3- (carbox-a-naphthylamide) furan; white flaky crystals; m.p. 151 ° C;

2,4 - dimethyl-3- (2-phenylcarboxanilide) fura; yellow viscous liquid with m. bale. 167-168 ° C / 0.02 mm Hg. v .;

2,4-dimethyl-3- (4-phenylcarboxanilide) furan; pale yellow powdery crystals; m.p. 238-242 ° C;

2,4 - dimethyl-3- (3-sodiumoxycarboxanilide) -furan; light brown powdered crystal; m.p. PO-170 ° C;

2,4-dimethyl - (0,5-kaly1; iy) -oxycarboxanilide-furan; light brown powdered crystals; m.p. 250 ° C; 2,4-dimethyl-3-3- (0,5-copper) -oxycarboxyl l; yd; -f; Wa. m.p. Above 290 ° С (change, colors at 210 ° С); ... i. , 4 - Dimet-Z-3- (0.5-zinc) -oxycarboxanilide-furan; white yorkhpkoobraznye

crystals; m.p. above 290 ° C;

 2,4-dimethyl- (0.5 - iron) -oxycarboxanilide-furan; white powdery crystals; m.p. 147 ° C;

2,4 - dimethyl-3- 3- (0,25 - tin) -oxycarboxanilide-furan; white powdery crystals; m.p. above 290 ° C;

2,4-dimethyl - (0,5-magnesium) -oxycarboxanilide-furan; brown powdery crystals; m.p. above 290 ° C.

Claims (1)

Invention Formula The method of obtaining 2,4-dimethyl-3-carboxanilide furan formula VOH. where X is the atom g of logen ;, alkyl, oxy-, ... .-. alkoxy, alkenyloxy-, alkynyl. oxygroup, .tryfluoromethyl, phenyl, cyano, acetyl; R is alkyl, alkenyl or alkynyl; n is an integer equal to O or 1, that is, and that the compound is general, to it the formulas NZS- || jpCONH- /  L 4V Tg P where X and p are as defined above; M is a hydrogen atom or an alkali metal, subjected to interaction with the compound of the general formula of the formula j, Y where R has the above meaning; Y is a halogen atom, in the medium of a solvent, and in the case when M is a hydrogen atom, the process is carried out in the presence of a base.