CS269683B1 - 2- (4-Tolylimino) 3-alkylidene indoles and methods for their preparation - Google Patents
2- (4-Tolylimino) 3-alkylidene indoles and methods for their preparation Download PDFInfo
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Abstract
Riešenie ea týká přípravy nových létok 2(4-tolylimino)-3-alkylidén indolov. všeobecného vzorca I, kde R znamená 4-Cl_CgH4, 4-Br-CgH4, 4-KO2CgH4, 3-^ 4-CN-CgíL· alebo 2-pytidyl. Podetata riašenia spočívá v tom, Že na 2-(4-tolylimino)- -3-trifenylfosfonium indolát vzorca II sa ' pžsobí aromatickými aldehydmi všeobecného ; vzorca III. kde R znamená 4-Cl, 4-Br, , 4_N02, 3-NO2 alebo 4-CN a I Je CH alebo R znamená H a a Je N v prostředí organických rozpúštadiel v rozmedzí tepldt O až 100 C Uvedené látky predstavujú nový a reaktivny typ heterocyklického azadienového systému, využitelného pre syntézu bioorganických zlúčenín indolu.The present invention relates to the preparation of new 2-(4-tolylimino)-3-alkylidene indoles of the general formula I, where R is 4-Cl-CgH4, 4-Br-CgH4, 4-KO2CgH4, 3-^ 4-CN-Cg1L· or 2-pyridyl. The invention consists in reacting 2-(4-tolylimino)- -3-triphenylphosphonium indolate of the formula II with aromatic aldehydes of the general formula III. where R is 4-Cl, 4-Br, 4-NO2, 3-NO2 or 4-CN and I is CH or R is H and a is N in an organic solvent environment at temperatures between 0 and 100 C. The substances mentioned represent a new and reactive type of heterocyclic azadiene system, usable for the synthesis of bioorganic indole compounds.
Description
CS 269 683 Bl 1
Vynález sa týká 2-(4-tolylimino)—3—alkylidénindolov všeobecného vzorca I
4-Br-CgH4, é-NOgCgH^, 3-RO2CgH^, 4-CR_CgH^ alebo 2-pyridil kde H 2načí 4-Cl_CgH^,a sp&sob ich přípravy.
Heterodiény sú doležitými komponentami Diels-Alderovýeh reakcií výaledkom kterýchaú heterocyklické zlúčeniny.
Stúdiom literatúry sa ukázalo, že 2)(4-telylimin«)-3-alkylidén indoly aú novými v li-ter! túře doteraz neopísanými zlúčenlnami.
Podstata spdsobu přípravy 2-(4-tolylimino)-3-alkylidénindolov spočívá v tom, že aana 2-(4-tolylimino)-3-trifenylfosíónium indolát vzorca II
(II)
p"oaobí aromatickými aldehydmi všeobecného vzorca III
(III) kde B'značí 4-Cl, 4-Br, 4-RO2, J-ROg alebo 4-CR, a X je CH alebo kde Rzznačí H a X je R (t.j. 2-pyridínkarbaldehyd) v prostředí organických rozpúStadiel v rozmedzí teplit 0-100 ®C. 2-(4-Tolylimino)-3-alkylidénindoly podlá vynálezu predatavujú nový a reaktívny typheterocyklického azadienového systému, Využitelného pre syntézu bioorganických žluče-ní n indolu.
Predmet vynálezu ilustrujú ale neobmedzujú náaledovné příklady! Příklad 1 K 4,85 g (0,01 mol) 2-(4-tolylimino)-3-trifenylfosfónium indolátu suspendovaného v100 ml metanolu sa přidá pri 50 °C 1,4 g (0,01 mol) 4-chlórbenzaldehydu. Zmes sa zah^rieva do úplného rozpustenia východzej látky. Po ukončení reakcie sa roztok zahustí napolovičný objem. Ochladením vykrištalizuje 2-(4-tolylimino)-3-(4-chlorbenzylidén)indolvo formě červených ihličiek. Výtažok 2,86 g čistej látky (83 %). Pyz.-chemické vlast-nosti sú uvedené v tabulce. 2 CS 269 683 Bl Příklad 2 K 4,85 g (0,01 mol) 2-(4-tolylimino)-3-trifenylfosfónium indolátu suspendovaného v50 ml etanolu sa přidá 1,4 g (0,01 mol) 4-kyanobenzaldehydu. Zmes sa mieSa a bahrievak varu pod sptítným chladl8om do úplného vySírenia roztoku. Po zahuštění a ochladeníreakénej zmesl krystalizuje 2-(4-tolylimino)-3-(4-kyanobenzylidén)indol vo formě tma-voServených ihiel. Výtažek 86 $>, Pyz.-chem. vlastnosti sú uvedené v tabuíke. Příklad 3 K 4,85 g (0,01 mol) 2-(4-tolylimino)-3-trifenylfosfórium indolátu suspendovaného v100 ml metylénchloridu sa přidá 1,07 g ¢0,01 mol) 2-pyridínkarbaldehydu a zmes sa zah-rieva k varu pod sptttným chladiSom až do úplného rozpustenia východzej zlúSeniny. Poofchladení a odpaření metylénchloridu ea zvySok krystalizuje z malého množstva etanolu.Výtažok 78 % fialovoServených kryStálov. Získané 2-(4-tolylimino)-3-alkylidénindoly sú Servené až fialové krystalické zlúSe-niny dobré rozpustné v organických rozpúStadlách (fyz.-chemické vlastnosti sú uvedenév tabuťke).
Spektrálné merania ΐδ spektrá sa namerali na spektrofotometr! IB 75 (Carl Zeiss Jena). XH NMR spektrábolí namerané na 100 MHz spektrometr! (Tesla BS 587). Hmotnostné spektrá bolí snímanéna spektrometrl MS 902S (AEI Manchester) pri 70 eV.
Tab. Pyzikálno-chemlcké vlastnosti 2-(4-tolylimino)-3-alkylidén indolov
ZlúSenlna R Vzorec (mol.h.) Výíažok {4(t.t.,°C) VypoSÍtané/zlatěné % c t H * N Ia 83 76,55 4,92 8,11 4-Cl-CgH4 (344,85) (180) 76,53 4,90 8,13 Ib ... 86 67,81 4,36 7,19 4-Br-CgH^ (389,30) <173) 67,83 4,34 7,21 Ic C221’l7n3°2 98 74,34 4,82 11,82 4-NO2-CgH4 (355,37) (215) 74,31 4,81 11,86 Id C22Hl7H3°2 72 74,34 4,82 11,82 3-N02-CgH4 (355,37) (182) 74,30 4,79 11,79 Ie C23H17N3 86 82,36 5,11 12,53 4-CN-C6H4 (335,38) (223) 82,33 5,10 12,55 If 78 81,00 5,50 13,49 2-pyridyl (311,36) (154) 81,03 5,48 13,52 2-(4-Tolylimino)-3-(4-chlórbenzylidén)-indol Ia Ιδ spektrum (KBr) t 3240 (st), 3050(sl), 2930(sl), 1640(sl), l600(st); 1598(s), 1524(s), 1445(st), 1400(st), 1326(st), 13O8(st), 1242(st), 1200(st), l08l(sl), 1008(s),8l5(st), XH NMR spektrum (DMSO-dg) : 2,50 s (CHj), 6,78-8,27 m (H-arom.), 9,25 d (NH).Hmotnostné spektrum (n^z, % rel. int.) 343(M+, 100), 330(6 , 307(19), 292(13), 233(32),218(22), 147(28). 2-(4-Tolylimino)-3-(4-brómbenzylidén)-indol Ib Ιδ spektrum (KBr) s 3250(st), 3040(sl), 2905(al), l64l(st), l602(sl), 1599(s), 1546(sl),1529(s), 1448(st), 1436(st), 1329(sl), 1307(st), 1246(sl), 1200(sl), 1120(st), 1000(sl),8O1(S1), 752(st). XH NMR spektrum (dg-BMSO) : 2,49 s (CH-j), 6,72-8,14 m (H-arom), 9,73 s(NH), Hmotnostné spektrum (m/z, % rel. int.) : 389(M+, 100), 387(90), 308(l6), 283(6),278(14), 235(20), 22l(l6), 218(5), 155(21), 106(22).
CS 269 683 B1 1
The invention relates to 2- (4-tolylimino) -3-alkylideneindoles of the general formula I
4-Br-CgH4, n-NOgCgH4, 3-RO2CgH4, 4-CR8H6, or 2-pyridine wherein H2al4 is a 4-C1-6H4, and a preparation thereof.
Heterodienes are important components of the Diels-Alder reactions, which are heterocyclic compounds.
It has been shown in the literature that 2) (4-thelylimine) -3-alkylidene indoles are new in the alkyl group. hitherto unrecorded compounds.
The process for the preparation of 2- (4-tolylimino) -3-alkylideneindoles is that the aana 2- (4-tolylimino) -3-triphenylphosphonium indole of formula II
(II)
p "is characterized by aromatic aldehydes of formula III
(III) wherein B 'is 4-Cl, 4-Br, 4-RO 2, J-ROg or 4-CR, and X is CH or wherein R 2 is H and X is R (ie 2-pyridinecarbaldehyde) in an organic solvent environment range to 0-100 ®C. According to the present invention, the 2- (4-Tolylimino) -3-alkylidenedoles predict a novel and reactive thymeterocyclic azadiene system useful for the synthesis of bioindic n-indole bile.
The subject matter of the invention is illustrated but not limited by the following examples. EXAMPLE 1 To 4.85 g (0.01 mol) of 2- (4-tolylimino) -3-triphenylphosphonium indolate suspended in 100 ml of methanol was added 1.4 g (0.01 mol) of 4-chlorobenzaldehyde at 50 ° C. The mixture is heated until complete dissolution of the starting material. After completion of the reaction, the solution is concentrated to half the volume. By cooling, 2- (4-tolylimino) -3- (4-chlorobenzylidene) indole is crystallized as red needles. Yield 2.86 g of pure material (83%). The chemical-chemical properties are shown in the table. EXAMPLE 2 To 4.85 g (0.01 mol) of 2- (4-tolylimino) -3-triphenylphosphonium indole, suspended in 50 ml of ethanol was added 4-cyanobenzaldehyde (1.4 g, 0.01 mol). The mixture is stirred and boiled under reflux until complete dissolution of the solution. After concentration and cooling of the reaction mixture, 2- (4-tolylimino) -3- (4-cyanobenzylidene) indole crystallized as dark red needles. Yield 86 $>, Pyz.-chem. the properties are given in the table. Example 3 To 4.85 g (0.01 mol) of 2- (4-tolylimino) -3-triphenylphosphorus indolate, suspended in 100 ml of methylene chloride, 1.07 g ¢ 0.01 mol of 2-pyridinecarbaldehyde was added and the mixture heated boiling under reflux until complete dissolution of the starting compound. Cooling and evaporation of methylene chloride and the residue crystallized from a small amount of ethanol. Yield 78% purple-red crystals. The obtained 2- (4-tolylimino) -3-alkylidenediols are servo-violet crystalline compounds which are soluble in organic solvents (physical properties are shown in the Table).
Spectral measurements of δδ spectra were measured on a spectrophotometer! IB 75 (Carl Zeiss Jena). 1 H NMR spectra measured on a 100 MHz spectrometer! (Tesla BS 587). Mass spectra were scanned by MS 902S (AEI Manchester) spectrometer at 70 eV.
Tab. Physico-chemical properties of 2- (4-tolylimino) -3-alkylidene indoles
Compound R Formula (mol.h.) Yield {4 (tt, ° C) Calculated / Gold% ct H * N Ia 83 76.55 4.92 8.11 4-Cl-CgH4 (344.85) (180) 76.53 4.90 8.13 Ib ... 86 67.81 4.36 7.19 4-Br-CgH ^ (389.30) <173) 67.83 4.34 7.21 Ic C221'l7n3 ° 2 98 74.34 4.82 11.82 4-NO2-CgH4 (355.37) (215) 74.31 4.81 11.86 Id C22H17H3 ° 2 72 74.34 4.82 11.82 3- NO2-CgH4 (355.37) (182) 74.30 4.79 11.79 Ie C23H17N3 86 82.36 5.11 12.53 4-CN-C6H4 (335.38) (223) 82.33 5, 10 12.55 If 78 81.00 5.50 13.49 2-pyridyl (311.36) (154) 81.03 5.48 13.52 2- (4-Tolylimino) -3- (4-chlorobenzylidene) -indole Ia spectrum (KBr) t 3240 (st), 3050 (sl), 2930 (sl), 1640 (sl), 1600 (st); 1598 (s), 1524 (s), 1445 (st), 1400 (st), 1326 (st), 13O8 (st), 1242 (st), 1200 (st), l08l (sl), 1008 (s), @ 1 H NMR (DMSO-d6): 2.50 s (CH2), 6.78-8.27 m (H-arom.), 9.25 d (NH). z,% rel. int.) 343 (M +, 100), 330 (6, 307 (19), 292 (13), 233 (32), 218 (22), 147 (28). 2- (4-Tolylimino) ) -3- (4-bromobenzylidene) -indole Ib umδ spectrum (KBr) s 3250 (st), 3040 (sl), 2905 (α1), 1641 (st), 1602 (sl), 1599 (s), 1546 ( sl), 1529 (s), 1448 (st), 1436 (st), 1329 (sl), 1307 (st), 1246 (sl), 1200 (sl), 1120 (st), 1000 (sl), 8o1 ( S1), 752 (st) .1H NMR Spectrum (d6-BMSO): 2.49 s (CH-1), 6.72-8.14 m (H-arom), 9.73 s (NH), Mass spectrum (m / z, rel. rel.): 389 (M +, 100), 387 (90), 308 (16), 283 (6), 278 (14), 235 (20), 22l (16), 218 (5), 155 (21), 106 (22).
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