Ищу реальную методику получения 5,10-диметилфеназина.
Все, что нашел, датируется 1957 годом и в обычной лаборатории довольно трудно воспроизводимо, тем более что необходимо получать его в довольно больших количествах. Буду очень благодарен за любую помощь
Получение 5,10-дигидро-5,10-диметилфеназена(DMPZ)
Re: Получение 5,10-дигидро-5,10-диметилфеназена(DMPZ)
о-Бромтолуол с N-метиланилином (как вариант) переводится в N-метил-N-фенил-о-толуидин. Далее, по классике, с серой в о-ксилоле кипятится, циклизуясь в нужный продукт.Михаил_Г писал(а):Ищу реальную методику получения 5,10-диметилфеназина.
Все, что нашел, датируется 1957 годом и в обычной лаборатории довольно трудно воспроизводимо, тем более что необходимо получать его в довольно больших количествах. Буду очень благодарен за любую помощь
Если я формулу понял правильно...
-=Jedem das Seine=-
Re: Получение 5,10-дигидро-5,10-диметилфеназена(DMPZ)
не правильно это будет фенотиазинSteiner писал(а):о-Бромтолуол с N-метиланилином (как вариант) переводится в N-метил-N-фенил-о-толуидин. Далее, по классике, с серой в о-ксилоле кипятится, циклизуясь в нужный продукт.Михаил_Г писал(а):Ищу реальную методику получения 5,10-диметилфеназина.
Все, что нашел, датируется 1957 годом и в обычной лаборатории довольно трудно воспроизводимо, тем более что необходимо получать его в довольно больших количествах. Буду очень благодарен за любую помощь
Если я формулу понял правильно...
DMPZ это диметилпиразол,
scifinder как beilstein эту охинею не поняли 5,10-дигидро-5,10-диметилфеназен. феназин это когда в фенотиазине заменить
Вам ведь нужно, нарисуйте формулу и поместите в exchange.
http://exchange.chemport.ru/index.php?m ... aaaaaa.bmp это оно?
Re: Получение 5,10-дигидро-5,10-диметилфеназена(DMPZ)
Да, опять моя невнимательность подвела.adolfina писал(а):не правильно это будет фенотиазинSteiner писал(а):о-Бромтолуол с N-метиланилином (как вариант) переводится в N-метил-N-фенил-о-толуидин. Далее, по классике, с серой в о-ксилоле кипятится, циклизуясь в нужный продукт.Михаил_Г писал(а):Ищу реальную методику получения 5,10-диметилфеназина.
Все, что нашел, датируется 1957 годом и в обычной лаборатории довольно трудно воспроизводимо, тем более что необходимо получать его в довольно больших количествах. Буду очень благодарен за любую помощь
Если я формулу понял правильно...
Я просто увидел слово знакомое... помнится пришлось однажды делать эти фенотиазины... 
-=Jedem das Seine=-
Re: Получение 5,10-дигидро-5,10-диметилфеназена(DMPZ)
to adolfina
Вам ведь нужно, нарисуйте формулу и поместите в exchange.
http://exchange.chemport.ru/index.php?m ... aaaaaa.bmp это оно?[/quote]
Да, это верная формула, а DMPZ перепутал с DMPH
Вам ведь нужно, нарисуйте формулу и поместите в exchange.
http://exchange.chemport.ru/index.php?m ... aaaaaa.bmp это оно?[/quote]
Да, это верная формула, а DMPZ перепутал с DMPH
Bibliographic Information
One pot synthesis of 5,10-dihydrophenazine compounds and 5,10-substituted dihydrophenazines. Giri, Punam; Byker, Harlan J.; Baumann, Kelvin L. (Gentex Corporation, USA). U.S. (2001), 12 pp. CODEN: USXXAM US 6242602 B1 20010605 Patent written in English. Application: US 99-280396 19990329. Priority: . CAN 135:20891 AN 2001:408067 CAPLUS
Patent Family Information
Patent No. Kind Date Application No. Date
US 6242602 B1 20010605 US 1999-280396 19990329
Priority Application
US 1999-280396 19990329
Abstract
Dihydrophenazines and bis(dihydrophenazines) are prepd. in high yield under com. viable reaction conditions by reacting a catechol with a 1,2-diaminoaryl compd., wherein either the catechol or the 1,2-diaminoaryl compd. is provided in at least 50% M stoichiometric excess. The product may be oxidized to the corresponding phenazine, but is preferably derivatized at one or both of the 5,10-positions to form a monosubstituted or disubstituted dihydrophenazine or bis(dihydrophenazine). Most preferably, 5,10-dialkyl-5,10-dihydrophenazines are prepd. starting from catechol and 1,2-diaminoaryl compd. in a one pot synthesis. The products are useful as dyes, and in particular as chromophores in electrochromic systems. Thus, 800 g 5,10-dihydrophenazine obtained from 1,2-diaminobenzene and catechol was mixed with 3.8 L acetonitrile, 275 g sodium dithionite, 868 g sodium carbonate, 1.2 L Me iodide, and 140 g methyltributylammonium chloride and heated to give 783 g 5,10-dimethyldihydrophenazine.
Patent Classifications
Main IPC: C07D241-46. U.S.: 544347000. Secondary IPC: C07D241-48.
Indexing -- Section 41-5 (Dyes, Organic Pigments, Fluorescent Brighteners, and Photographic Sensitizers)
Section cross-reference(s): 28
Aromatic compounds
Role: RCT (Reactant); RACT (Reactant or reagent)
(1,2-diamino derivs.; one pot synthesis of 5,10-(substituted)dihydrophenazine compds. by reaction of catechols with 1,2-diaminoaryl compds.)
Azines
Role: IMF (Industrial manufacture); PREP (Preparation)
(5,10-(substituted)dihydrophenazines; one pot synthesis of 5,10-(substituted)dihydrophenazine compds. by reaction of catechols with 1,2-diaminoaryl compds.)
Acylation
(agents; one pot synthesis of 5,10-(substituted)dihydrophenazine compds. by reaction of catechols with 1,2-diaminoaryl compds.)
Sulfonates
Role: RCT (Reactant); RACT (Reactant or reagent)
(alkanesulfonates, alkylation agents; one pot synthesis of 5,10-(substituted)dihydrophenazine compds. by reaction of catechols with 1,2-diaminoaryl compds.)
Polyoxyalkylenes, uses
Role: NUU (Other use, unclassified); USES (Uses)
(alkyl group-terminated, oligomeric, solvents; one pot synthesis of 5,10-(substituted)dihydrophenazine compds. by reaction of catechols with 1,2-diaminoaryl compds.)
Alkylation
(alkylating agents; one pot synthesis of 5,10-(substituted)dihydrophenazine compds. by reaction of catechols with 1,2-diaminoaryl compds.)
Alkyl halides
Role: RCT (Reactant); RACT (Reactant or reagent)
(alkylation agents; one pot synthesis of 5,10-(substituted)dihydrophenazine compds. by reaction of catechols with 1,2-diaminoaryl compds.)
Sulfates, reactions
Role: RCT (Reactant); RACT (Reactant or reagent)
(dialkyl, alkylating agents; one pot synthesis of 5,10-(substituted)dihydrophenazine compds. by reaction of catechols with 1,2-diaminoaryl compds.)
Polyoxyalkylenes, uses
Role: NUU (Other use, unclassified); USES (Uses)
(oligomeric, solvents; one pot synthesis of 5,10-(substituted)dihydrophenazine compds. by reaction of catechols with 1,2-diaminoaryl compds.)
Phase transfer catalysts
Reducing agents
(one pot synthesis of 5,10-(substituted)dihydrophenazine compds. by reaction of catechols with 1,2-diaminoaryl compds.)
Flavanols
Role: RCT (Reactant); RACT (Reactant or reagent)
(one pot synthesis of 5,10-(substituted)dihydrophenazine compds. by reaction of catechols with 1,2-diaminoaryl compds.)
Onium compounds
Role: RCT (Reactant); RACT (Reactant or reagent)
(oxonium, trialkyl, alkylating agents; one pot synthesis of 5,10-(substituted)dihydrophenazine compds. by reaction of catechols with 1,2-diaminoaryl compds.)
Glycols, uses
Role: NUU (Other use, unclassified); USES (Uses)
(solvents; one pot synthesis of 5,10-(substituted)dihydrophenazine compds. by reaction of catechols with 1,2-diaminoaryl compds.)
74-88-4, Methyl iodide, reactions
Role: RCT (Reactant); RACT (Reactant or reagent)
(alkylating agent; one pot synthesis of 5,10-(substituted)dihydrophenazine compds. by reaction of catechols with 1,2-diaminoaryl compds.)
613-32-1P, 5,10-Dihydrophenazine
342906-51-8P
342906-53-0P
Role: IMF (Industrial manufacture); RCT (Reactant); PREP (Preparation); RACT (Reactant or reagent)
(intermediate; one pot synthesis of 5,10-(substituted)dihydrophenazine compds. by reaction of catechols with 1,2-diaminoaryl compds.)
92-82-0P, Phenazine
15546-75-5P
_
342903-88-2P
342903-90-6P
342903-91-7P
342903-92-8P
342903-93-9P
342903-94-0P
342903-95-1P
342903-96-2P
342903-97-3P
342906-52-9P
342906-54-1P
342906-55-2P
342906-56-3P
342908-63-8P
Role: IMF (Industrial manufacture); PREP (Preparation)
(one pot synthesis of 5,10-(substituted)dihydrophenazine compds. by reaction of catechols with 1,2-diaminoaryl compds.)
342903-87-1P
342903-89-3P
Role: IMF (Industrial manufacture); RCT (Reactant); PREP (Preparation); RACT (Reactant or reagent)
(one pot synthesis of 5,10-(substituted)dihydrophenazine compds. by reaction of catechols with 1,2-diaminoaryl compds.)
65712-00-7P
219756-67-9P
361533-77-9P
361533-78-0P
Role: IMF (Industrial manufacture); RCT (Reactant); SPN (Synthetic preparation); PREP (Preparation); RACT (Reactant or reagent)
(one pot synthesis of 5,10-(substituted)dihydrophenazine compds. by reaction of catechols with 1,2-diaminoaryl compds.)
219756-75-9P
219756-80-6P
303982-87-8P
361534-22-7P
361534-36-3P
Role: IMF (Industrial manufacture); SPN (Synthetic preparation); PREP (Preparation)
(one pot synthesis of 5,10-(substituted)dihydrophenazine compds. by reaction of catechols with 1,2-diaminoaryl compds.)
91-95-2, 3,3'-Diaminobenzidine
95-54-5, 1,2-Diaminobenzene, reactions
98-29-3, 4-tert-Butylcatechol
120-80-9, Catechol, reactions
452-86-8, 4-Methylcatechol
488-17-5, 3-Methylcatechol
496-72-0, 3,4-Diaminotoluene
Role: RCT (Reactant); RACT (Reactant or reagent)
(one pot synthesis of 5,10-(substituted)dihydrophenazine compds. by reaction of catechols with 1,2-diaminoaryl compds.)
361533-57-5P
Role: SPN (Synthetic preparation); PREP (Preparation)
(one pot synthesis of 5,10-(substituted)dihydrophenazine compds. by reaction of catechols with 1,2-diaminoaryl compds.)
56375-79-2, Methyltributylammonium chloride
Role: CAT (Catalyst use); USES (Uses)
(phase transfer catalyst; one pot synthesis of 5,10-(substituted)dihydrophenazine compds. by reaction of catechols with 1,2-diaminoaryl compds.)
7775-14-6, Sodium dithionite
Role: NUU (Other use, unclassified); USES (Uses)
(reducing agent; one pot synthesis of 5,10-(substituted)dihydrophenazine compds. by reaction of catechols with 1,2-diaminoaryl compds.)
75-05-8, Acetonitrile, uses
107-21-1, Ethylene glycol, uses
Role: NUU (Other use, unclassified); USES (Uses)
(solvent; one pot synthesis of 5,10-(substituted)dihydrophenazine compds. by reaction of catechols with 1,2-diaminoaryl compds.)
Supplementary Terms
hydrophenazine one pot synthesis catechol aminoaryl compd
Citations
Waterman; US 2292808 1942
Soule; US 2332179 1943
Anon; JP 5095281 1975
Morley, J; J Chem Soc 1952, 4008
Henry, G; Journal of American Chemical Society 1957, 79, 6178
Bettinetti, G; Synthesis 1976, 748
Mikhailov, B; Metal Compounds of Phenazine and Their Transformations 1950, 44, 9452
Axel, K; Chem Ber 1992, 125, 1495
Akira, S; Preparation and Properties of Electron Donor Acceptor Complexes of the Compounds Having Capto-Dative Substituents 1989, 26, 435
Bibliographic Information
Direct preparation of some dihydro and other phenazine derivatives. Gilman, Henry; Dietrich, Joseph J. Iowa State Coll., Ames, Journal of the American Chemical Society (1957), 79 6178-9. CODEN: JACSAT ISSN: 0002-7863. Journal language unavailable. CAN 52:35301 AN 1958:35301 CAPLUS
Abstract
Phenazine (I)(3.6 g.), 1.7 g. K, and 25 cc. (CH3OMe)2 stirred 10.5 hrs., treated with excess MeI and then with EtOH, decompd. with satd. aq. NH4Cl, and distd. left 2.5 g. 5,10-dimethyl-5,10-dihydrophenazine (II), m. 153-5°(EtOH). I (9 g.), 1 g. Li, and 50 cc. tetrahydrofuran refluxed 4.5 hrs., treated with excess MeI, and worked up in the usual manner gave only 62% unchanged I. PhLi (0.06 mole) in 60 cc. Et2O added to 9 g. I in 60 cc. tetrahydrofuran during 15 min. at room temp., stirred 0.5 hr., treated with 8.5 g. MeI, stirred 2 hrs. at room temp. and hydrolyzed with dil. HCl, and the resulting solid (7.3 g.) chromatographed from C6H6 on Al2O3 yielded 5 g. 5-methyl-10-phenyl-5,10-dihydrophenazine (III), m. 116-17° (EtOH). PhLi (0.06 mole) in 65 cc. Et2O added during 15 min. to 9 g. I in 65 cc. tetrahydrofuran, stirred 3.5 hrs. at room temp., and treated with 15.3 g. PhI, 1 g. Cu powder, and 70 cc. kerosene, the lower boiling solvents distd., the residual mixt. heated 12 hrs. at 210°, the kerosene distd., and the residue dissolved in C6H6 and chromatographed on Al2O3 yielded 4.2 g. 5,10-di-Ph analog (IV) of II, pale yellow needles, m. 283-5° (C6H6-ligroine, b. 60-70°). IV (2 g.), 0.33 g. Li, and 10 cc. tetrahydrofuran refluxed 3 days, treated with 14.2 g. MeI, and filtered through glass wool, the solvent evapd., and the residue dissolved in C6H6 and chromatographed on Al2O3 yielded 0.3 g. III, m. 116-18° (EtOH). III (1.5 g.), 0.33 g. Li, and 10 cc. tetrahydrofuran refluxed 3 days with stirring and treated with 14.2 g. MeI, the solvent distd., and the residue chromatographed gave 0.4 g. II, m. 154-6° (EtOH). (Ph2N)2 (5.5 g.) and 25 cc. dry PhMe refluxed 0.5 hr. under N and chromatographed on Al2O3, the eluate distd., and the yellow oily distillate boiled with EtOH-Me2CO did not give a pure product. MeLi (0.053 mole) in 60 cc. Et2O added to 9 g. I in 60 cc. tetrahydrofuran during 15 min. at room temp., stirred 15 min., treated with 11 g.
MeI, and hydrolyzed with H2O, and the Et2O layer worked up yielded 0.2 g. II; the mother liquor yielded 0.4 g. unidentified product, needles, m. 125-7°. PhMgBr (0.06 mole) in 60 cc. Et2O added to 9 g. I in 80 cc. tetrahydrofuran at room temp. with stirring during 1.75 hrs., treated with excess MeI, and hydrolyzed with dil. HCl, the solvent distd., and the residue chromatographed from C6H6 on Al2O3 yielded 2 g. unchanged I. I (9 g.), 32 g. Br, and 100 cc. glacial AcOH refluxed 13 hrs. with stirring and dild. with dil. NH4OH gave 0.4 g. tetrabromophenazine, green-yellow needles, m. 340-1° (pyridine). I (9 g.), 10.4 g. Ac2O, 20 g. AlCl3, and 75 cc. (CHCl2)2 stirred 5.25 hrs. at 140° and hydrolyzed with dil. HCl and the org. layer washed with dil. aq. Na2CO3 and evapd. yielded only 6.2 g. pure I.
Indexing -- Section 10 (Organic Chemistry)
92-82-0, Phenazine
(and derivs.)
3665-72-3, Phenazine, 5,10-dihydro-5,10-diphenyl-
15546-75-5, Phenazine, 5,10-dihydro-5,10-dimethyl-
_
15546-77-7, Phenazine, 5,10-dihydro-5-methyl-10-phenyl-
117072-31-8, Phenazine, tetrabromo-
(prepn. of)
One pot synthesis of 5,10-dihydrophenazine compounds and 5,10-substituted dihydrophenazines. Giri, Punam; Byker, Harlan J.; Baumann, Kelvin L. (Gentex Corporation, USA). U.S. (2001), 12 pp. CODEN: USXXAM US 6242602 B1 20010605 Patent written in English. Application: US 99-280396 19990329. Priority: . CAN 135:20891 AN 2001:408067 CAPLUS
Patent Family Information
Patent No. Kind Date Application No. Date
US 6242602 B1 20010605 US 1999-280396 19990329
Priority Application
US 1999-280396 19990329
Abstract
Dihydrophenazines and bis(dihydrophenazines) are prepd. in high yield under com. viable reaction conditions by reacting a catechol with a 1,2-diaminoaryl compd., wherein either the catechol or the 1,2-diaminoaryl compd. is provided in at least 50% M stoichiometric excess. The product may be oxidized to the corresponding phenazine, but is preferably derivatized at one or both of the 5,10-positions to form a monosubstituted or disubstituted dihydrophenazine or bis(dihydrophenazine). Most preferably, 5,10-dialkyl-5,10-dihydrophenazines are prepd. starting from catechol and 1,2-diaminoaryl compd. in a one pot synthesis. The products are useful as dyes, and in particular as chromophores in electrochromic systems. Thus, 800 g 5,10-dihydrophenazine obtained from 1,2-diaminobenzene and catechol was mixed with 3.8 L acetonitrile, 275 g sodium dithionite, 868 g sodium carbonate, 1.2 L Me iodide, and 140 g methyltributylammonium chloride and heated to give 783 g 5,10-dimethyldihydrophenazine.
Patent Classifications
Main IPC: C07D241-46. U.S.: 544347000. Secondary IPC: C07D241-48.
Indexing -- Section 41-5 (Dyes, Organic Pigments, Fluorescent Brighteners, and Photographic Sensitizers)
Section cross-reference(s): 28
Aromatic compounds
Role: RCT (Reactant); RACT (Reactant or reagent)
(1,2-diamino derivs.; one pot synthesis of 5,10-(substituted)dihydrophenazine compds. by reaction of catechols with 1,2-diaminoaryl compds.)
Azines
Role: IMF (Industrial manufacture); PREP (Preparation)
(5,10-(substituted)dihydrophenazines; one pot synthesis of 5,10-(substituted)dihydrophenazine compds. by reaction of catechols with 1,2-diaminoaryl compds.)
Acylation
(agents; one pot synthesis of 5,10-(substituted)dihydrophenazine compds. by reaction of catechols with 1,2-diaminoaryl compds.)
Sulfonates
Role: RCT (Reactant); RACT (Reactant or reagent)
(alkanesulfonates, alkylation agents; one pot synthesis of 5,10-(substituted)dihydrophenazine compds. by reaction of catechols with 1,2-diaminoaryl compds.)
Polyoxyalkylenes, uses
Role: NUU (Other use, unclassified); USES (Uses)
(alkyl group-terminated, oligomeric, solvents; one pot synthesis of 5,10-(substituted)dihydrophenazine compds. by reaction of catechols with 1,2-diaminoaryl compds.)
Alkylation
(alkylating agents; one pot synthesis of 5,10-(substituted)dihydrophenazine compds. by reaction of catechols with 1,2-diaminoaryl compds.)
Alkyl halides
Role: RCT (Reactant); RACT (Reactant or reagent)
(alkylation agents; one pot synthesis of 5,10-(substituted)dihydrophenazine compds. by reaction of catechols with 1,2-diaminoaryl compds.)
Sulfates, reactions
Role: RCT (Reactant); RACT (Reactant or reagent)
(dialkyl, alkylating agents; one pot synthesis of 5,10-(substituted)dihydrophenazine compds. by reaction of catechols with 1,2-diaminoaryl compds.)
Polyoxyalkylenes, uses
Role: NUU (Other use, unclassified); USES (Uses)
(oligomeric, solvents; one pot synthesis of 5,10-(substituted)dihydrophenazine compds. by reaction of catechols with 1,2-diaminoaryl compds.)
Phase transfer catalysts
Reducing agents
(one pot synthesis of 5,10-(substituted)dihydrophenazine compds. by reaction of catechols with 1,2-diaminoaryl compds.)
Flavanols
Role: RCT (Reactant); RACT (Reactant or reagent)
(one pot synthesis of 5,10-(substituted)dihydrophenazine compds. by reaction of catechols with 1,2-diaminoaryl compds.)
Onium compounds
Role: RCT (Reactant); RACT (Reactant or reagent)
(oxonium, trialkyl, alkylating agents; one pot synthesis of 5,10-(substituted)dihydrophenazine compds. by reaction of catechols with 1,2-diaminoaryl compds.)
Glycols, uses
Role: NUU (Other use, unclassified); USES (Uses)
(solvents; one pot synthesis of 5,10-(substituted)dihydrophenazine compds. by reaction of catechols with 1,2-diaminoaryl compds.)
74-88-4, Methyl iodide, reactions
Role: RCT (Reactant); RACT (Reactant or reagent)
(alkylating agent; one pot synthesis of 5,10-(substituted)dihydrophenazine compds. by reaction of catechols with 1,2-diaminoaryl compds.)
613-32-1P, 5,10-Dihydrophenazine
342906-51-8P
342906-53-0P
Role: IMF (Industrial manufacture); RCT (Reactant); PREP (Preparation); RACT (Reactant or reagent)
(intermediate; one pot synthesis of 5,10-(substituted)dihydrophenazine compds. by reaction of catechols with 1,2-diaminoaryl compds.)
92-82-0P, Phenazine
15546-75-5P
_
342903-88-2P
342903-90-6P
342903-91-7P
342903-92-8P
342903-93-9P
342903-94-0P
342903-95-1P
342903-96-2P
342903-97-3P
342906-52-9P
342906-54-1P
342906-55-2P
342906-56-3P
342908-63-8P
Role: IMF (Industrial manufacture); PREP (Preparation)
(one pot synthesis of 5,10-(substituted)dihydrophenazine compds. by reaction of catechols with 1,2-diaminoaryl compds.)
342903-87-1P
342903-89-3P
Role: IMF (Industrial manufacture); RCT (Reactant); PREP (Preparation); RACT (Reactant or reagent)
(one pot synthesis of 5,10-(substituted)dihydrophenazine compds. by reaction of catechols with 1,2-diaminoaryl compds.)
65712-00-7P
219756-67-9P
361533-77-9P
361533-78-0P
Role: IMF (Industrial manufacture); RCT (Reactant); SPN (Synthetic preparation); PREP (Preparation); RACT (Reactant or reagent)
(one pot synthesis of 5,10-(substituted)dihydrophenazine compds. by reaction of catechols with 1,2-diaminoaryl compds.)
219756-75-9P
219756-80-6P
303982-87-8P
361534-22-7P
361534-36-3P
Role: IMF (Industrial manufacture); SPN (Synthetic preparation); PREP (Preparation)
(one pot synthesis of 5,10-(substituted)dihydrophenazine compds. by reaction of catechols with 1,2-diaminoaryl compds.)
91-95-2, 3,3'-Diaminobenzidine
95-54-5, 1,2-Diaminobenzene, reactions
98-29-3, 4-tert-Butylcatechol
120-80-9, Catechol, reactions
452-86-8, 4-Methylcatechol
488-17-5, 3-Methylcatechol
496-72-0, 3,4-Diaminotoluene
Role: RCT (Reactant); RACT (Reactant or reagent)
(one pot synthesis of 5,10-(substituted)dihydrophenazine compds. by reaction of catechols with 1,2-diaminoaryl compds.)
361533-57-5P
Role: SPN (Synthetic preparation); PREP (Preparation)
(one pot synthesis of 5,10-(substituted)dihydrophenazine compds. by reaction of catechols with 1,2-diaminoaryl compds.)
56375-79-2, Methyltributylammonium chloride
Role: CAT (Catalyst use); USES (Uses)
(phase transfer catalyst; one pot synthesis of 5,10-(substituted)dihydrophenazine compds. by reaction of catechols with 1,2-diaminoaryl compds.)
7775-14-6, Sodium dithionite
Role: NUU (Other use, unclassified); USES (Uses)
(reducing agent; one pot synthesis of 5,10-(substituted)dihydrophenazine compds. by reaction of catechols with 1,2-diaminoaryl compds.)
75-05-8, Acetonitrile, uses
107-21-1, Ethylene glycol, uses
Role: NUU (Other use, unclassified); USES (Uses)
(solvent; one pot synthesis of 5,10-(substituted)dihydrophenazine compds. by reaction of catechols with 1,2-diaminoaryl compds.)
Supplementary Terms
hydrophenazine one pot synthesis catechol aminoaryl compd
Citations
Waterman; US 2292808 1942
Soule; US 2332179 1943
Anon; JP 5095281 1975
Morley, J; J Chem Soc 1952, 4008
Henry, G; Journal of American Chemical Society 1957, 79, 6178
Bettinetti, G; Synthesis 1976, 748
Mikhailov, B; Metal Compounds of Phenazine and Their Transformations 1950, 44, 9452
Axel, K; Chem Ber 1992, 125, 1495
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Bibliographic Information
Direct preparation of some dihydro and other phenazine derivatives. Gilman, Henry; Dietrich, Joseph J. Iowa State Coll., Ames, Journal of the American Chemical Society (1957), 79 6178-9. CODEN: JACSAT ISSN: 0002-7863. Journal language unavailable. CAN 52:35301 AN 1958:35301 CAPLUS
Abstract
Phenazine (I)(3.6 g.), 1.7 g. K, and 25 cc. (CH3OMe)2 stirred 10.5 hrs., treated with excess MeI and then with EtOH, decompd. with satd. aq. NH4Cl, and distd. left 2.5 g. 5,10-dimethyl-5,10-dihydrophenazine (II), m. 153-5°(EtOH). I (9 g.), 1 g. Li, and 50 cc. tetrahydrofuran refluxed 4.5 hrs., treated with excess MeI, and worked up in the usual manner gave only 62% unchanged I. PhLi (0.06 mole) in 60 cc. Et2O added to 9 g. I in 60 cc. tetrahydrofuran during 15 min. at room temp., stirred 0.5 hr., treated with 8.5 g. MeI, stirred 2 hrs. at room temp. and hydrolyzed with dil. HCl, and the resulting solid (7.3 g.) chromatographed from C6H6 on Al2O3 yielded 5 g. 5-methyl-10-phenyl-5,10-dihydrophenazine (III), m. 116-17° (EtOH). PhLi (0.06 mole) in 65 cc. Et2O added during 15 min. to 9 g. I in 65 cc. tetrahydrofuran, stirred 3.5 hrs. at room temp., and treated with 15.3 g. PhI, 1 g. Cu powder, and 70 cc. kerosene, the lower boiling solvents distd., the residual mixt. heated 12 hrs. at 210°, the kerosene distd., and the residue dissolved in C6H6 and chromatographed on Al2O3 yielded 4.2 g. 5,10-di-Ph analog (IV) of II, pale yellow needles, m. 283-5° (C6H6-ligroine, b. 60-70°). IV (2 g.), 0.33 g. Li, and 10 cc. tetrahydrofuran refluxed 3 days, treated with 14.2 g. MeI, and filtered through glass wool, the solvent evapd., and the residue dissolved in C6H6 and chromatographed on Al2O3 yielded 0.3 g. III, m. 116-18° (EtOH). III (1.5 g.), 0.33 g. Li, and 10 cc. tetrahydrofuran refluxed 3 days with stirring and treated with 14.2 g. MeI, the solvent distd., and the residue chromatographed gave 0.4 g. II, m. 154-6° (EtOH). (Ph2N)2 (5.5 g.) and 25 cc. dry PhMe refluxed 0.5 hr. under N and chromatographed on Al2O3, the eluate distd., and the yellow oily distillate boiled with EtOH-Me2CO did not give a pure product. MeLi (0.053 mole) in 60 cc. Et2O added to 9 g. I in 60 cc. tetrahydrofuran during 15 min. at room temp., stirred 15 min., treated with 11 g.
MeI, and hydrolyzed with H2O, and the Et2O layer worked up yielded 0.2 g. II; the mother liquor yielded 0.4 g. unidentified product, needles, m. 125-7°. PhMgBr (0.06 mole) in 60 cc. Et2O added to 9 g. I in 80 cc. tetrahydrofuran at room temp. with stirring during 1.75 hrs., treated with excess MeI, and hydrolyzed with dil. HCl, the solvent distd., and the residue chromatographed from C6H6 on Al2O3 yielded 2 g. unchanged I. I (9 g.), 32 g. Br, and 100 cc. glacial AcOH refluxed 13 hrs. with stirring and dild. with dil. NH4OH gave 0.4 g. tetrabromophenazine, green-yellow needles, m. 340-1° (pyridine). I (9 g.), 10.4 g. Ac2O, 20 g. AlCl3, and 75 cc. (CHCl2)2 stirred 5.25 hrs. at 140° and hydrolyzed with dil. HCl and the org. layer washed with dil. aq. Na2CO3 and evapd. yielded only 6.2 g. pure I.
Indexing -- Section 10 (Organic Chemistry)
92-82-0, Phenazine
(and derivs.)
3665-72-3, Phenazine, 5,10-dihydro-5,10-diphenyl-
15546-75-5, Phenazine, 5,10-dihydro-5,10-dimethyl-
_
15546-77-7, Phenazine, 5,10-dihydro-5-methyl-10-phenyl-
117072-31-8, Phenazine, tetrabromo-
(prepn. of)
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