SU591145A3 - Method of preparing 2,4-dimethyl-3-carboxyanilidefuran derivatives or salts thereof - Google Patents

Description

LINES or tertichitms, for example, triethylamine, trimetidamnn, dimegilaniline, tilaniline, tfidii, N-methylmorphine, as well as sodium carbonate, cadium carbonate, sodium carbonate, etc. Benzene, toluene, xylene, apeton, methyl platinum, ether, dioxane, acegonitrile, dichloroethane are used as inert solvents. П РИМ ep 1. Preparation of 2,4-dnmethyl-3- (2-methylcarboxanilide-furan. In 100 ml of benzene with stirring and cooling with ice water pacTBopsnoT 10.7 (0.1 mol) O-toluidine and 10.1 g (ODMo triethylamine, then 20 ml of benzene is added dropwise to the solution while stirring to the leg of a solution containing 15.8 g (0.1m o of 2,4-dimethyl-3-furoyl chloride, since this reaction is exothermic, the temperature is kept inside the mixture no more than 20 ° C. Next, the cooling bath is removed and the reaction is continued at room temperature for 2 hours. Then the mixture is washed with water, diluted with hydrochloric acid, water, 5% one 4 "1 solution of sodium bicarbonate and water. The product is dehydrated with anhydrous sodium sulfate, the benzene is distilled off. and the remaining solid is recrystallized from a mixture of benzene and n-hexane (1: 2) to obtain 18.4 g (80.3%) Target product with mp 130-132 ° C in the form of pink crista allov. Pr and measures 2. Preparation of 2,4-Dimethyl No. 3- (3-methylcarboxanyl e) furan. In 10 ml of acetone are dissolved 10.7 g (0.1 mol) m -toluidine; then, with stirring, 8.4 g (0.1 mol) of sodium biKaji6oHaTa is added, the solution is cooled with ice water and 2 O ml of acetone solution is added dropwise to the mixture Containing 15.8 g (O 1 mole) of 2,4-dimethyl-W-furoyl chloride. A weakly ecoacothermic 1cake with gaseous carbon dioxide is emitted. Then the cooling bath is removed and the reaction is carried out at room temperature for 2 hours. The mixture is poured into water, the precipitated O1-filter is drained and dried, then the lane is crystallized from a mixture of benzene and n-hexane (1: 2) to obtain 20.4 g (88.2%) of nepev product with m.p .: 117,5118 C in the form of light yellow crystals. IR spectrum (tablets of CB g), cm: VKJJ 5250 (S) v 1650 S, 1660 S P p and m er 3. Preparation of 2,4-dimethyl 3- (3.5 and methylcarboxanilide) furan, B. 12 O ml of ether while stirring and cooling with ice water, 12.1 g (0.1 mol) of 3,5-xylidine and 7.9 g (0.1 ml) of pyridine are dissolved, then 2 O m of ether are added to the mixture according to: qgp m with stirring a solution containing 15.8 g, (0.1 mol) 2,4-dimothyl 3-furoyl chloride, as this reaction is acothermic, t ("." nejjaTypy inside the mixture is kept not higher than 20 C. After termination and addition the reaction is performed at room temperature for 2 hours. Then the mixture is washed with water, diluted hydrochloric acid, water, an aqueous solution of sodium bicarbonate and water. The product is dehydrated with anhydrous sodium sulfate, the ether is distilled off and the residue is recrystallized; splued from methanol, giving 19.6 g (80.6%) of the desired product as light yellow flaky crystals, mp 149152 ° C. Example 4. Preparation of 2,4-dimesh-1-3 (2-ethylcarboxanilide) furan. 12.1 g (od mol) O are dissolved in 100 ml of benzene under stirring and cooling with ice water. | -ethaniline and 12.1 g (0.1 mol) K, K -dimethylaniline, then 2 O ml of benzene solution is added dropwise with stirring, containing 15.8 g (OD mol) of 2,4-dimethyl-3-furoyl chloride, as the exothermic reaction proceeds, inside the mixture the temperature is kept no higher than 20 C. After the addition is completed, the mixture is gradually heated to 40 ° C and the reaction is carried out for 1 hour at 40 C. After cooling, the mixture is washed with water, dilute hydrochloric acid, water, 5% aqueous sodium bicarbonate solution and water. The product is dehydrated with anhydrous sodium sulfate, the benzene is distilled off, and the residue is recrystallized from 9O% methanol to obtain 21.0 g (86.5%) of the desired product as a white powder, mp. 108-111 ° C. PRI me R 5. Obtaining 2,4-dimeti№-3- (3-oxasharboxanilide) -furan. 1 O, 9 g (0.1 mol) of 3-o-sianiline is dissolved in 150 ml of acetone, 8.4 g (0.1 mol) of sodium bicarbonate is added to the mixture, cooled and then added dropwise with stirring 15.9 g (0.1 mol) of 2,4-dimethyl-3-furoyl chloride. The mixture is then stirred at room temperature for 5 hours, poured onto ice water and acidified with dilute hydrochloric acid. & The fallen crystals are filtered, washed with water and dried, then recrystallized from a mixture of methanol and water to give 21.3 g (92.0%) of the desired product, in the form of white crystals, m.p. 147-148 C. Example 6. Preparation of 2,4-dimethyl- 3- (2-ethoxycarboxanylpd) furan. In 1OO ml of benzene, 13.7 g (0.1 mol) of 2-ethoxyaniline and 7.9 g (O, 1 mol) of pyridine are dissolved, cooled in ice water, i is added dropwise to the mixture with stirring and temperature not more than 2 O With 20 ml of benzene solution containing 15.8 g (0.1 mol) 2,4-dimetid-3-}) uroig chloride. 1b .. the reaction is continued at a condensation temperature of 2 h. Then the mixture is filled with water (1 water, dilute hydrochloric acid, water: 5% aqueous sodium bicarbonate solution and water. The product is dehydrated with anhydrous sodium sulfate, benzene distilled and solid suspended into recrystallization from 90% methanol, obtaining 23., O g (88.7%) of the target product in the form of light yellow needle-like crystals, mp 71.5-73.5 C. P EXAMPLE 7 Preparation of 2,4-dimethyl No. 3- (3-meter-x-carboxanilide) -4) uranium. 12.3 g (0.1 mn) of m-anisidine HJ are dissolved in 100 ml of acetone 8.4 g (0.1 mop of sodium bicarbonate and cooled with ice-cold water, then 2 O ml of acetone are added dropwise with stirring solution, 15.8 g (0.1 mol) of 2,4-dimethyl-3-furoyl chloride, because the reaction is exothermic, the temperature of the mixture is not higher than 20 ° C. After the addition is complete, the reaction is carried out at room temperature for 2 hours, then the mixture Poured into 20 ml of water, the precipitated crystals are filtered, dried and recrystallized from a mixture of benzene and n-hexane (l: 2) to obtain 23.0 g (93.9%) of the desired product as white. x flake crystals, mp 120-123 C. Example: Preparation of 2,4-dimethyl-3- (2,5-dimethox-carboxanilide) furan: In 120 ml of benzene with stirring and cooling with ice water dissolved 15 , 3 g (0.1 mop) of 2,5-yimethoxyaniline and 10.1 (0.1 mol) of triethylamine, then 2 O ml of a benzene solution containing 15.8 g (0.1 mol) is added dropwise with stirring. ) 2,4-dimethyl-3-furoigosloride, since the reaction is exothermic, the temperature of the mixture is kept no higher than 20 ° C. After the addition is completed, the reaction is continued at room temperature for 2 hours, then the mixture is washed with water, diluted hydrochloric acid, water, 5%; - aqueous aqueous solution of sodium bixonate and water. The product is dried with anhydrous sodium sulfate, the benzene is distilled off, the remaining solid product is recrystallized from methanol, yielding 22.8 g (83%) of the desired product as gray crystals,. m.p. 90-92 C. Example 9. Preparation of 2,4-dimethyl-3- (2-methoxy-5-methylcarboxanilide) furan na. In 150 MP of acetone, while stirring and cooling with ice water, 13.7 g (0.1 mol) of 2-methoxy-5-methylaniline and 12.1 g (0.1 mol) of M, 1T-dimethylaniline, then are dissolved. 20 ml of an acetone solution containing 15.8 g of 0.1 mol of 2,4-dimethyl-3-furoyl chloride are added dropwise, because the reaction is exothermic, the temperature is kept no higher than 20 ° C. The mixture is then gradually heated to 50 ° C and the reaction is carried out at 50 ° C for 1 hour, cooled, poured into 400 ml of water, the precipitated crystals are filtered off, dried and recrystallized from n-hexane, yielding 22.3 g (86.2%) of the desired .product in the form of light brown crystals, so pl. 77.5-78.5 C. Example 10. Preparation of 2,4-dimethyl-3- (2-chlorocarboxanilide) furan. Under stirring and cooling with ice water, 100 ml of benzene dissolved 12.8 g (o, 1 mol) of O-chloroaniline and 10.1 g (o, 1 mol) of triethylamine, then added dropwise with stirring 2, 0 ml of benzene solution containing 15.9 g (O, 1 mol) of 2,4-dimethyl-3C) uroyl chloride. After the addition is complete, the reaction is continued at room temperature for 2 hours, then the mixture is washed with water, diluted with hydrochloric acid, water, 5% aqueous sodium bicarbonate and water; the benzene is distilled off and the solid product is recrystallized from methanol to obtain 21.3 g (85%) of the desired product as pale yellow needle-like crystals, m.p. 108-109 C, EXAMPLE 11. Preparation of 2,4-dimethyl-3- (3-chlorocarboxanilide) -4uran. 12.8 g (0.1 mol) of M-chloroaniline and 8.4 g (0.1 mol) of sodium bicarbonate are dissolved in 70 ml of acetone, the mixture is cooled with ice water and 20 ml of acetone solution are added dropwise with P1 stirring coaef containing 15.8 g (0.1 mol) of 2,4-dimethyw 3 -pyroylchloride, since the reaction i aK3OTej Ulic, generate carbon dioxide. At the end of the addition, the reaction is carried out at room temperature for 2 hours, then the mixture is poured into 20 ml of water and the precipitated product is filtered, dried and recrystallized. lysing from a mixture of ligroin and carbon tetrachloride (| 4: l) to obtain 2O, 4 g (82%) of the desired product in the form of light yellow powdery crystals, mp. 114117 C. P p: AND M er 12. Preparation of 2,4-dimethyl- 3- (4-bromocarboxanilide) -4 Uran. Under cooling with ice water and stirring, 1 ml of benzene dissolved 17.2 g (0.1 mol) of 4-bromoaniline and 12.1 g (0.1 mol) of CK-dimethylaniline, then added dropwise with stirring. ml of benzene solution containing 15.8 g (0.1 mol) of 2,4-dimethyl-3-furoyl chloride. At the end of the addition, the mixture is heated gradually and. the reaction is carried out at 40 ° C for 1 h, then cooled, washed with water, dilute hydrochloric acid, 5% aqueous sodium bicarbonate solution and water, benzene is distilled off and the solid product is recrystallized from methanol to obtain 24.5 g (83.5 %) of the target product in the form of needles, so pl. 159-160 S.

Example 13. Getting 2,4-dime-. Ti / L-3 (2,4-dichlorocarboxyanilide) -4) uranium.

16.2 g (0.1 mol) of 2,4-dichlororanipine and 7.9 g (OD mol) of pyridine are dissolved in 120 ml of ether with stirring and cooling with ice water, then 20 ml of ether are added dropwise with stirring. a solution containing 15.8 g (0.1 mol) of 2,4-dimethyl-3-furoylchporide, since the reaction is exothermic, the temperature of the mixture is kept no higher than 20 C. After the addition is completed, the reaction is carried out at room temperature for 2 hours, then the product is washed are diluted with hydrochloric acid, Vova, 5% sodium bicarbonate solution. The ether is distilled off and the solid product is recrystallized from 1) ethanol to obtain 22.4 g (79%) of the non-base product in the form of light yellow thin particles with crystals, m.p. 88.5-90 C.

Example 14. Semi-Junior 2.4 "dimethyl-3- (2-methyl-3-chlorocarboxanilide) furan.

14.1 g (O, 1 mol) of 2-methyl-3-chloroalkyl and 8.4 g (od mol) of sodium bicarbonate are dissolved in 7O ml of acetone, the mixture is cooled with ice water, then 20 are added dropwise with stirring. ml of acetone solution containing 15.8 g (0.1 mol of 2,4-diamethyl-3-furoyl chloride. A slightly exothermic reaction proceeds with separation of carbon dioxide gas. After the addition is complete, the reaction is carried out at room temperature for 2 hours, then the mixture is poured into 20O ml of water, the precipitated product is filtered; Washed, washed with methanol, dried, and 22.7 g (86.6%) of the desired product was obtained. e a white powder, m.p. 128-132 C.

Example 15. Preparation of 2,4-Dimethyl-3- (3-trifluoromethylcarboxanilide) furan.

16 D g (o, 1 mol) A-trifluoromethylaniline and 7.9 g (o, 1 mol) pyridine are dissolved in 150. ml of benzene, the mixture is cooled with ice water, then 20 ml of benzene solution is added dropwise with stirring , contains 15.9 g (0.1 mol) of 2,4-dimethyl-3-furoyl chloride. After the addition is complete, the reaction is continued at room temperature for 2.5 hours with stirring, then the mixture is washed with water to remove pyridine hydrochloride, dried with anhydrous sodium sulfate, the benzene is distilled off and 28.3 g of a brown product is obtained, which

eight

recrystallized from a mixture of methanol and water to obtain 27.0 g (96%) of the desired product as yellow needle-shaped cristaps. t.pl.103-104.5 ° C.

PRI me R 16. Getting 2,4-dimethyl. - 3- (2-hlrr-.5-trifluoromethylcarboxanilide) furan.

19.5 g (0.1 mol) of 2-chloro 5-trifluoromethylaniline and 8.4 g (o, 1 mol) of sodium bicarbonate are dissolved in 100 ml of acetone, the mixture is cooled with ice water and added dropwise with stirring 30 ml of acetone solution of 15.8 g (0.1 mol) of 2,4-dimethyl-3-furoyl chloride. There is a weak exotherm; there is a physical reaction with the release of gas-forming carbon dioxide. At the end of the addition, the reaction is continued at room temperature, 2.5 hours, the mixture is poured into 500 ml of water and the precipitated product is filtered, dried and recrystallized from methanol to obtain 25.4 g (80.2%) of the desired product as white needle-like crystals. m.p. ; i 1: 2-115s.

Example 17. Obtaining 2,4-dimethyl-3- (2-phenylcarboxanil e) .- furan.

16.9 g (o, 1 mol) of O-bifenylamine and 10.1 g (o, mol) of triethyamine are dissolved in 20 O ml of benzene, cooled with icy water, then 15.9 are added dropwise to the mixture with stirring g (mol of 2,4-dimethyl-3-furoyl chloride. After the addition is complete, the mixture is stirred at room temperature for 3 hours, the product is washed with water, dilute hydrochloric acid and water, dried with anhydrous sodium sulfate. After distillation of benzene, the product is distilled under vacuum, obtaining 25.8 g (88.6%) of the desired product as a yellow viscous liquid, bp 167-168 C / O, O2 mm Hg.

Example 18. Preparation of 2,4-dimethyl 3- (carbox-c. Naphthylamide) furan.

14.3 g (o, 1 mol / oCg-naphthalylamine and 8.4 g (o, 1 mol) sodium bicarbonate are dissolved in 150 ml (acetone), then 15.9 are added dropwise to the mixture while stirring at room temperature. g (0.1 mol) 2,4-dimethyl-3-h {uroyl chloride. After the addition is complete, the mixture is stirred for 3 hours, poured into 80 ml of water, the precipitated product is filtered off and recrystallized from methanol, to obtain 24.5 g (92.3% %) of the desired product in the form of white flociform crystals, mp 151 C

The table shows compounds obtained in a similar way.

9

ten

2,4-Dimvtil-3 (4-methylcarbovsvil a) furan

2.4 Dnmtip-3 (2,3-dnmetilkir. 6ox shsha) furvn

2,4-11vmetnp 3- (2,4 pvmet lka {bodanshnga p)

2,4-D) imv (2,5-dimethylcar6oxane lead) 4 uran

2,4-Dimvtyp-3 (3,4-dnmvtyylkaroksvnEpid) - furan

2.4 "Dimethyl 3- (2.4 in Trimvgvlkar6r Savilid) - furan

2,4 Dimethyl-3- (2-hydroxycar6ox kilide) furan

2,4-.Dimetvl "3- (4-oxivar6oxanil furan

2,4-Dimethyl-.3- (2-methoxyn-6-oxanilide). Urav

2,4-Dimeti №-3- (4-methoxycarbo & Sanvlid) "- furan

2,4-.Dnmvtil 3- (2-ETOXI-.5-methi.Caroxannlide) uranium

2,4-Dimetgo1-3- (2 1ropoxy-5-mwt lkarboxansh d) -h)) uranium

2,4-Dimethyl-3- (2-n-propnloksika1 boksanilid) furvn

2,4-D imethyl-Z- (2-isopropylox carboxanilide) -furan

127.5-128

156-158

1O8-112

144-147

111-114

174-175

170-171

e

186-187

you are e

62-63

you are e

133-134

White crystals

79

62-63

e

51-53

138-141 / 0.008

AND

2,4-Dimethyl-3- (2-n-butyloxyka boksanipv a) -furan

2,4-Dimetip-3- (2-apshgaksikarboxanipid) -furan

2,4- 1 metip-3 (Zn-aropnpoksikarbokokanipid) -furan

2.4 Dimetip-3 (3-isopropyloxy 1 boksanipia) -4 uran

2,4-Dimetip-.3- (3- & uxyloxycarboxanilide) -4uran

2, 4 Dimetvp 3 (3 n-hexyloxanecarbxanilide) -furan

2.4-D | 1metsh1 Zg (3-in-octEpoxycarbo

sainlid) furan ,,

2,5-jQHMeTiui-3- (3-allv rksvkarbok-

Sanilid) - fura

2,4-Dimethylx3- (3 "pc 1sargyloxscar boksanilid) -furan.

2,4-Dimeti Z (4 «« lorkar6oxav lead) -furan

2,4-Dimmtyp-3- (2-methyl "4-" LOR1SH1. Boxanil e) Wagon

2,4-Dimetvp-Z- (2-tr tormetvlkarboxanilvd)

2,4-Dimvtil-3- (4-1shankarboksanilvd) uranium

2.4 Dvmetil-3- (4-acetylcarboxanil) -C | uranium

32

Continued tablishl

spruce needles

68,5-69 Ristaly

Elias peristo 59.0-59,5

scandals

Ristillas

windswept

117-118 crystalline crystals

Light brown 80-82 neva crystals

Light-measles. new ones

124-125 chat room

White needles122-123 th crystals

White needles 117-119 crystals

White crystals 114-115 ly

White crystals109-111 ly

White needles 101-103 th crystals

Red-brown cristae} 81, 5-85 ly powder of a different type

Light yellow

102-110 / 0.15

transparent

liquid

Brown 1e 14O-142 needles

Pale yellow

needles

146-147

crystals

13

Compound

2,4t. Dimethyl-3- (4-phenylcarboxane lead) -fishing

2,4-D imethyl- 3- (3-on triyoxycarbo

sanshgad) furan

2,4-Dimetsh1-3- | z- (0.5 calpium) oxncarboxanilide .4uran

2,4-Dimegil-3- {s- (0.5 copper), carboxanilide-4uran

2,4-Dimethyl-3- | 3- (0.5 shgak) -oxv. carboxanilide | -furan

2,4-Dimvtil-3 "- | s (0.5 iron) oxus rboxane or wounds

2,4-Dimetip-3- 3- (0.25 tin) oxycarboxanil flj-furan

Claims (1)

1.PL., bp, C / mm pr.fT 238-242 110-170 25O Above 290 Vyp 290 147  29O Above 290 de T1 - 1–3, or X is a group of atoms that donor a condensed benzene ring, provided that 11 –2, or their salts, is of a kind, and the compounds of the general formula COHai II, where Hat is a halogen, is subjected to interaction with the compound of the general formula 15, where X and iimey specified values, in the presence of dehydrog-a / jugenprook. an organic base agent, for example, triethipamine, or an inorganic agent, for example sodium carbonate, in an er; de inert organic solvent, for example benzene, followed by isolation of the target product in free form or in the form of a salt. 59.1 11 r P5. 2. According to Claim. 1, about tl and h “w sh and and so. This issue is carried out by a pi of 20–50 pp. reduced by reference. Sources of information taken into account at the examination: 1. Bgoler K., Pearson D. Organic syntheses. M., 1973, v. 2, p. 388.