1,3 диацетилинден
1,3 диацетилинден
Никто не встречал приличных обзоров по химии индена? Требуется получить различные 1,3 дизамещенные индены, например, диацетил, диформил, дикарбоксиэтил. Как-то не получается у меня найти более или менее систематизированный материал.
Необходимость преодоления собственного интеллектуального ничтожества есть необходимое и достаточное ограничение в доступе к научной информации
Craig, J. Cymerman; Dinner, Alan; Mulligan, Patrick J. Simplified analogs of lysergic acid. V. Derivatives of N,N-diethyl-1-methyl-9H-indeno-1,2,3,9a-tetrahydro[2,1-b]pyridine-3-carboxamide. Journal of Organic Chemistry (1974), 39(12), 1669-76
1-Acetylindene (loa), l,3-Diacetylindene (lob), and 3,3-Uiacetylindene
(9). Acetyl bromide (12.3 g, 0.1 M) was added slowly
to indenyllithium, prepared from indene (12.5 g, 0.1075 mol) and
n-butyllithium (62.5 ml, 1.6 M, 0.1 mol) in hexane (62.5 ml) and
ether (75 ml). The reaction mixture was refluxed for 30 min,
cooled, and diluted with water. The ethereal layer was washed
with brine, dried (MgS04), filtered, and evaporated under reduced
pressure to yield an oil. Chromatography on silicic acid
gave three compounds. On elution with 2% ethanol in pentane,
1,3-diacetylindene (lob, 2.5 g, 15%) was obtained as an oil: ir
(neat) 1750 (saturated ester +O), 1680 cm-* (conjugated ester
-0); nmr (CDC13) S 7.5 (m, 1 H, aromatic), 7.1 (m, 3 H, aromatic),
6.7-6.4 (m, 2 H), 2.3 (5, 3 H, COCHs), 2.1 (s, 3 H,
Anal. Calcd for C13H1202: C, 77.98; H, 6.04. Found: C, 77.51,
H, 6.35.
Elution with 3% ethanol in pentane gave 1-acetylindene, mp
52-54" (1.3 g, 9%). Recrystallization from pentane gave a sample:
mp 67-68"; ir (CHC13) 1675 cm-' (conjugated e o ) ; nmr
(CDC13) 6 8.1 (m, 1 H, aromatic H), 7.15 (m, 4 H, three aromatic
and one olefinic H), 3.23 (m, 2 H, allylic methylene protons), 2.25
(s, 3 H, CH3).
Anal. Calcd for C1IHloO: C! 83.51; ; H, 6.43. Found: C, 83.65; ;
H, 6.66.
Further elution with 5% ethanol in pentane yielded 3,3-diacetylindene
(200 mg, 1%). Recrystallization from ether-pentane
gave a sample: mp 90-90.5"; ir (Nujol) 1725 and 1700 cm-1 (saturated
C=O); nmr (CDC13) 6 7.52 (m, 1 H, aromatic H), 7.38 (m,
3 H, aromatic H), 6.77 (dd, 2 H, olefinic H), and 1.96 (s, 6 H,
methyl H).
Anal. Calcd for C13H1202: C, 77.98; H, 6.04. Found: C, 78.15;
Bibliographic Information
Synthetic reactions of dimethylformamide. XXII. Formation and preparation of formyl derivatives of indene. Arnold, Z. Ceskoslov. Akad. Ved, Prague, Collection of Czechoslovak Chemical Communications (1965), 30(8), 2783-92. CODEN: CCCCAK ISSN: 0010-0765. Journal written in English. CAN 63:54472 AN 1965:454472 CAPLUS
Abstract
cf. CA 62, 7628b, 7670e. Similarly as described earlier (CA 56, 15328g), 0.19 g. 1,4-C6H4(CH2CO2H)2 gave, when heated with the formylation agent from 0.54 ml. POCl3 and 2.2 g. HCONMe2 6 hrs. at 90°, the mixt. decompd. with ice, and 0.42 g. NaClO4 added, 4.3 g. salt I [R1 = H, R2 = (Me2NCH:CCHNMe2)+ClO4-], m. 301-4° (H2O), which yielded, on heating with satd. K2CO3 soln. 1 hr. on a boiling water bath, extg. the mixt. with 2:1 C6H6EtOH, evapg. the solvents and heating the org. material 5 min. with M NaOH, 60% II, m. 320°. Analogously, 1,3-C6H4(CH2CO2H)2 gave 65% I [R1 = (Me2NCH:CCH: NMe2)+ClO4-, R2 = H], m. 214-16° (H2O), whereas formylation of 1,2-C6H4(CH2CO2H)2 gave a mixt. of products which was identified III (R1 = CHO, R2 = H), m. 162-3.5°. Indene (23.2 g.) in 50 ml. CHCl3 added with ice-cooling to 100 ml. 2M soln. of Me2N:CHCl (CA 53, 4112c) in CHCl3 and the mixt. kept 4 days gave 5.88 g. 2-indenecarboxaldehyde (IV), m. 49-50.5°; oxime m. 128-30°. Direct formylation of IV failed, but 5.8 g. IV was treated with 8.6 ml. HCO2Et, 12 ml. abs. EtOH, and 80 mg. NH4NO3 and the next day with anhyd. K2CO3 and the obtained diethyl acetal (V) (8.3 g.), b0-3 85-8° n20D 1.5250, treated with Me2NH.HClO4 to yield 93% dimethyl-2-indolylmethyleneammonium perchlorate, m. 167.5-72° (1:3 MeCN-dioxane). In the presence of excess formylation agent, indene gave at 90° for 3 hrs. 55% 1,2,3-triformylindene, m. 147-9°. Analogously were prepd. 66% III [R1 = R2 = (CH:NMe2)+ClO4-] m. 216-20° (1:2 MeCN-AcOH), 80.5% III [R11 or R2 = CHO, R2 or R11 = (CH:NMe2)+ClO4-], m. 189-92° (MeCN), 89% III (R1 = R2 = H), m. 87.92° (cyclohexane, CCl4), III [R1 = (CH:NMe2)+ClO4-, R2 = H], m. 310-12° (1:1 MeCN-H2O). 1,3-Diformylindene obtained in 90% yield by condensing indene with 1,1-dimethoxytrimethylamine (VI) gave crystals, m. 198-200° (MeCN-H2O), and 1.1 g. V heated with 5 ml. VI and 10 ml. PhMe at 140° yielded by the usual treatment 0.61 g. III [R1 = H, R2 = (CH:NMe2)+ClO4-], m. 202-6° (4:1 dioxaneMeCN). Formylation of 3.96 g.
2-indanone as above afforded 9.9 g. III [R1 = (CH:NMe2)+ClO4-, R2 = Cl], m. 185-7° (MeCN), yielding in the presence of HNMe2 III [R1 = (CH:NMe2)+ClO4-, R2 = NMe2], decompg. 160-4° (1:3 MeCNEtOH), which, in turn, gave with satd. K2CO3 in a C6H6-EtOHH2O mixt. III (R1 = CHO, R2 = NMe2), m. 147-53° (CCl4). 1,3-Bis(dimethylaminomethylene)-2-indanone obtained by condensing 2-indanone with VI gave crystals, m. 142-7° (CCl4). The course of the above-mentioned reactions is discussed.
1-Acetylindene (loa), l,3-Diacetylindene (lob), and 3,3-Uiacetylindene
(9). Acetyl bromide (12.3 g, 0.1 M) was added slowly
to indenyllithium, prepared from indene (12.5 g, 0.1075 mol) and
n-butyllithium (62.5 ml, 1.6 M, 0.1 mol) in hexane (62.5 ml) and
ether (75 ml). The reaction mixture was refluxed for 30 min,
cooled, and diluted with water. The ethereal layer was washed
with brine, dried (MgS04), filtered, and evaporated under reduced
pressure to yield an oil. Chromatography on silicic acid
gave three compounds. On elution with 2% ethanol in pentane,
1,3-diacetylindene (lob, 2.5 g, 15%) was obtained as an oil: ir
(neat) 1750 (saturated ester +O), 1680 cm-* (conjugated ester
-0); nmr (CDC13) S 7.5 (m, 1 H, aromatic), 7.1 (m, 3 H, aromatic),
6.7-6.4 (m, 2 H), 2.3 (5, 3 H, COCHs), 2.1 (s, 3 H,
Anal. Calcd for C13H1202: C, 77.98; H, 6.04. Found: C, 77.51,
H, 6.35.
Elution with 3% ethanol in pentane gave 1-acetylindene, mp
52-54" (1.3 g, 9%). Recrystallization from pentane gave a sample:
mp 67-68"; ir (CHC13) 1675 cm-' (conjugated e o ) ; nmr
(CDC13) 6 8.1 (m, 1 H, aromatic H), 7.15 (m, 4 H, three aromatic
and one olefinic H), 3.23 (m, 2 H, allylic methylene protons), 2.25
(s, 3 H, CH3).
Anal. Calcd for C1IHloO: C! 83.51; ; H, 6.43. Found: C, 83.65; ;
H, 6.66.
Further elution with 5% ethanol in pentane yielded 3,3-diacetylindene
(200 mg, 1%). Recrystallization from ether-pentane
gave a sample: mp 90-90.5"; ir (Nujol) 1725 and 1700 cm-1 (saturated
C=O); nmr (CDC13) 6 7.52 (m, 1 H, aromatic H), 7.38 (m,
3 H, aromatic H), 6.77 (dd, 2 H, olefinic H), and 1.96 (s, 6 H,
methyl H).
Anal. Calcd for C13H1202: C, 77.98; H, 6.04. Found: C, 78.15;
Bibliographic Information
Synthetic reactions of dimethylformamide. XXII. Formation and preparation of formyl derivatives of indene. Arnold, Z. Ceskoslov. Akad. Ved, Prague, Collection of Czechoslovak Chemical Communications (1965), 30(8), 2783-92. CODEN: CCCCAK ISSN: 0010-0765. Journal written in English. CAN 63:54472 AN 1965:454472 CAPLUS
Abstract
cf. CA 62, 7628b, 7670e. Similarly as described earlier (CA 56, 15328g), 0.19 g. 1,4-C6H4(CH2CO2H)2 gave, when heated with the formylation agent from 0.54 ml. POCl3 and 2.2 g. HCONMe2 6 hrs. at 90°, the mixt. decompd. with ice, and 0.42 g. NaClO4 added, 4.3 g. salt I [R1 = H, R2 = (Me2NCH:CCHNMe2)+ClO4-], m. 301-4° (H2O), which yielded, on heating with satd. K2CO3 soln. 1 hr. on a boiling water bath, extg. the mixt. with 2:1 C6H6EtOH, evapg. the solvents and heating the org. material 5 min. with M NaOH, 60% II, m. 320°. Analogously, 1,3-C6H4(CH2CO2H)2 gave 65% I [R1 = (Me2NCH:CCH: NMe2)+ClO4-, R2 = H], m. 214-16° (H2O), whereas formylation of 1,2-C6H4(CH2CO2H)2 gave a mixt. of products which was identified III (R1 = CHO, R2 = H), m. 162-3.5°. Indene (23.2 g.) in 50 ml. CHCl3 added with ice-cooling to 100 ml. 2M soln. of Me2N:CHCl (CA 53, 4112c) in CHCl3 and the mixt. kept 4 days gave 5.88 g. 2-indenecarboxaldehyde (IV), m. 49-50.5°; oxime m. 128-30°. Direct formylation of IV failed, but 5.8 g. IV was treated with 8.6 ml. HCO2Et, 12 ml. abs. EtOH, and 80 mg. NH4NO3 and the next day with anhyd. K2CO3 and the obtained diethyl acetal (V) (8.3 g.), b0-3 85-8° n20D 1.5250, treated with Me2NH.HClO4 to yield 93% dimethyl-2-indolylmethyleneammonium perchlorate, m. 167.5-72° (1:3 MeCN-dioxane). In the presence of excess formylation agent, indene gave at 90° for 3 hrs. 55% 1,2,3-triformylindene, m. 147-9°. Analogously were prepd. 66% III [R1 = R2 = (CH:NMe2)+ClO4-] m. 216-20° (1:2 MeCN-AcOH), 80.5% III [R11 or R2 = CHO, R2 or R11 = (CH:NMe2)+ClO4-], m. 189-92° (MeCN), 89% III (R1 = R2 = H), m. 87.92° (cyclohexane, CCl4), III [R1 = (CH:NMe2)+ClO4-, R2 = H], m. 310-12° (1:1 MeCN-H2O). 1,3-Diformylindene obtained in 90% yield by condensing indene with 1,1-dimethoxytrimethylamine (VI) gave crystals, m. 198-200° (MeCN-H2O), and 1.1 g. V heated with 5 ml. VI and 10 ml. PhMe at 140° yielded by the usual treatment 0.61 g. III [R1 = H, R2 = (CH:NMe2)+ClO4-], m. 202-6° (4:1 dioxaneMeCN). Formylation of 3.96 g.
2-indanone as above afforded 9.9 g. III [R1 = (CH:NMe2)+ClO4-, R2 = Cl], m. 185-7° (MeCN), yielding in the presence of HNMe2 III [R1 = (CH:NMe2)+ClO4-, R2 = NMe2], decompg. 160-4° (1:3 MeCNEtOH), which, in turn, gave with satd. K2CO3 in a C6H6-EtOHH2O mixt. III (R1 = CHO, R2 = NMe2), m. 147-53° (CCl4). 1,3-Bis(dimethylaminomethylene)-2-indanone obtained by condensing 2-indanone with VI gave crystals, m. 142-7° (CCl4). The course of the above-mentioned reactions is discussed.
Re: 1,3 диацетилинден
1H-indene-1,3-dicarboxylic acid diethyl ester
Novikov, Alexei V.; Kennedy, Abigail R.; Rainier, Jon D.; JOCEAH; J. Org. Chem.; EN; SIR68; 3; 2003; 993 - 996.
чисто 1,3-диформилинден не ищется
Novikov, Alexei V.; Kennedy, Abigail R.; Rainier, Jon D.; JOCEAH; J. Org. Chem.; EN; SIR68; 3; 2003; 993 - 996.
чисто 1,3-диформилинден не ищется
Спасибо большое, а раскройте секрет, пожалуйста, где и как вы ищите и есть ли туда доступ открытый, хотя бы к абстрактам?
Чехшские методики я уже пробовал. А вот остальное посмотрю, если не сложно, можно H-indene-1,3-dicarboxylic acid diethyl ester
Novikov, Alexei V.; Kennedy, Abigail R.; Rainier, Jon D.; JOCEAH; J. Org. Chem.; EN; SIR68; 3; 2003; 993 - 996.
в эксчендж.
Чехшские методики я уже пробовал. А вот остальное посмотрю, если не сложно, можно H-indene-1,3-dicarboxylic acid diethyl ester
Novikov, Alexei V.; Kennedy, Abigail R.; Rainier, Jon D.; JOCEAH; J. Org. Chem.; EN; SIR68; 3; 2003; 993 - 996.
в эксчендж.
Необходимость преодоления собственного интеллектуального ничтожества есть необходимое и достаточное ограничение в доступе к научной информации
Ага, я там тему отдельную под это дело завел http://chemport.ru/guest2/viewtopic.php?t=6284
Необходимость преодоления собственного интеллектуального ничтожества есть необходимое и достаточное ограничение в доступе к научной информации
Кто сейчас на конференции
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