메뉴 건너뛰기




Volumn , Issue 11, 2007, Pages 1695-1698

Conversion of azobenzenes into N,N′-diarylhydrazines by sodium dithionite

Author keywords

Azobenzenes; Hydrazines; Reduction; Sodium dithionite

Indexed keywords

2,2,4,4,6,6 HEXAMETHYLAZOBENZENE; 4,4 DIMETHOXYAZOBENZENE; AZO COMPOUND; AZOBENZENE DERIVATIVE; BENZENE DERIVATIVE; HYDRAZINE; SODIUM DITHIONITE; UNCLASSIFIED DRUG;

EID: 34447532438     PISSN: 09365214     EISSN: None     Source Type: Journal    
DOI: 10.1055/s-2007-982565     Document Type: Article
Times cited : (13)

References (77)
  • 7
    • 34447519237 scopus 로고
    • Blatt, A. H, Ed, Wiley and Sons: New York
    • Fieser, L. F. In Organic Syntheses, Coll. Vol. II; Blatt, A. H., Ed.; Wiley and Sons: New York, 1943, 35.
    • (1943) Organic Syntheses, Coll , vol.2 , pp. 35
    • Fieser, L.F.1
  • 9
    • 0343282568 scopus 로고
    • Horning, E. C, Ed, Wiley and Sons: New York
    • (b) Redemann, C. T.; Redemann, C. E. In Organic Syntheses, Coll. Vol. III; Horning, E. C., Ed.; Wiley and Sons: New York, 1955, 69.
    • (1955) Organic Syntheses, Coll , vol.3 , pp. 69
    • Redemann, C.T.1    Redemann, C.E.2
  • 10
    • 34447529391 scopus 로고
    • Stickstoffverbindungen II, Amine
    • Müller, E, Ed, Georg Thieme Verlag: Stuttgart
    • (c) Schröter, R.; Möller, F. Stickstoffverbindungen II, Amine In Methoden der Organischen Chemie (Houben-Weyl), Vol. XI/1; Müller, E., Ed.; Georg Thieme Verlag: Stuttgart, 1957, 437.
    • (1957) Methoden der Organischen Chemie (Houben-Weyl) , vol.XI 1 , pp. 437
    • Schröter, R.1    Möller, F.2
  • 27
    • 34447519236 scopus 로고    scopus 로고
    • A number of methods are available for the synthesis of azobenzenes from various nitrogen-containing benzene derivatives. See: (a) Schündehü tte, K. H. Stickstoffverbindungen I In Methoden der Organischen Chemie Houben-Weyl, X/3; Müller, E, Stroh, R, Eds, Georg Thieme Verlag: Stuttgart, 1965, 371
    • A number of methods are available for the synthesis of azobenzenes from various nitrogen-containing benzene derivatives. See: (a) Schündehü tte, K. H. Stickstoffverbindungen I In Methoden der Organischen Chemie (Houben-Weyl), Vol. X/3; Müller, E.; Stroh, R., Eds.; Georg Thieme Verlag: Stuttgart, 1965, 371.
  • 28
    • 34447532459 scopus 로고
    • Organische Stickstoffverbindungen IV
    • Klamann, D, Ed, Georg Thieme Verlag: Stuttgart
    • (b) Lang-Fugmann, S. Organische Stickstoffverbindungen IV In Methoden der Organischen Chemie (Houben-Weyl), Vol. E16d; Klamann, D., Ed.; Georg Thieme Verlag: Stuttgart, 1992, 66.
    • (1992) Methoden der Organischen Chemie (Houben-Weyl) , vol.E16d , pp. 66
    • Lang-Fugmann, S.1
  • 49
    • 34447506604 scopus 로고    scopus 로고
    • General Procedure for the Preparation of Azobenzenes 1a-k from Anilines Oxygen was bubbled through a mixture of an aniline derivative (20 mmol, CuCl)2 (0.20 g, 2.0 mmol, and dry pyridine (20 mL, which was stirred at r.t. for 1-3 h. The reaction was quenched by addition of H 2O (20 mL, which in some cases gave a precipitate, in other cases not. When no precipitate was formed, the hydrolyzate was extracted with Et 2O (3 x 10 mL) and the combined extracts were dried (MgSO 4, filtered, and concentrated on a rotary evaporator. Purification by flash chromatography (silica, hexane-EtOAc in a ratio of 90:10) gave a solid, which was recrystallized from EtOH and dried under vacuum. When the azobenzene precipitated during the hydrolysis, the precipitate was filtered, washed with H2O on the filter, and dried under vacuum. The products were characterized by IR, 1H NMR, and 13C NMR spectroscopy, mass spectromet
    • 13C NMR spectroscopy, mass spectrometry, and melting points (when appropriate), which were compared with literature data.
  • 50
    • 34447526808 scopus 로고    scopus 로고
    • All the products were known from the literature: 1a [29418-34-6]: ref. 8k, 8m; 1b [29418-25-5]: ref. 8f, 8g, 8j; 1c [29418-31-3]: ref. 8f, 8g, 8i, 8k, 8m; 1d [77611-71-3]: ref. 8c, 8r, 8s; 1e [5692-66-0]: ref. 61, 8d, 8e, 8g, 8h; 1f [7334-33-0]: ref. 8k, 8m, 8p, 8t, 8u, 8v; 1g [15426-14-9]: ref. 8k, 8m, 8n, 8p, 8q, 8t; 1h [1602-00-2]: ref. 8f, 8g, 8j-m, 8p, 8q, 8s, 8t; 1i [613-55-8]: ref. 8k, 8m, 8n, 8p, 8t, 8u; 1j [6319-23-9]: ref. 8t, 8u, 8v; 1k [501-58-6]: ref. 8j, 8k-m, 8o, 8p, 8u.
    • All the products were known from the literature: 1a [29418-34-6]: ref. 8k, 8m; 1b [29418-25-5]: ref. 8f, 8g, 8j; 1c [29418-31-3]: ref. 8f, 8g, 8i, 8k, 8m; 1d [77611-71-3]: ref. 8c, 8r, 8s; 1e [5692-66-0]: ref. 61, 8d, 8e, 8g, 8h; 1f [7334-33-0]: ref. 8k, 8m, 8p, 8t, 8u, 8v; 1g [15426-14-9]: ref. 8k, 8m, 8n, 8p, 8q, 8t; 1h [1602-00-2]: ref. 8f, 8g, 8j-m, 8p, 8q, 8s, 8t; 1i [613-55-8]: ref. 8k, 8m, 8n, 8p, 8t, 8u; 1j [6319-23-9]: ref. 8t, 8u, 8v; 1k [501-58-6]: ref. 8j, 8k-m, 8o, 8p, 8u.
  • 51
    • 34447530954 scopus 로고    scopus 로고
    • General Procedure for the Reduction of Azobenzenes to N,N′-Diarylhydrazines Azobenzene 1 (0.4-2.1 mmol) was added to a mixture of H2O (165 mL/mmol of 1, MeOH (165 mL/mmol of 1, and CH2Cl2 (25 mL/mmol of 1, The resulting mixture was stirred and heated to reflux, and an excess of sodium dithionite (see Table 1) was added. After stirring at reflux (see Table 1, the product mixture was poured into ice and extracted with Et2O (3 x 100 mL, The combined extracts were dried (MgSO4) and filtered, and then the solvent was removed under reduced pressure to give a residue, from which the product 2 was isolated by flash chromatography silica, hexane-EtOAc in a ratio of 90:10, The results are compiled in Table 1
    • 4) and filtered, and then the solvent was removed under reduced pressure to give a residue, from which the product 2 was isolated by flash chromatography (silica, hexane-EtOAc in a ratio of 90:10). The results are compiled in Table 1.
  • 52
    • 34447544597 scopus 로고    scopus 로고
    • All the N,N′-diarylhydrazines except 2,2′,4,4′- tetramethyl-(N,N′-diphenylhydrazine, 2b) are mentioned several times in the literature: 2a [107418-14-4, ref. 8c, 8m, 13f, 13j; 2c [63615-06-5, ref. 8m, 13f; 2d [142068-90-4, ref. 8c; 2e [5692-66-0, ref. 8m, 13a; 2f [782-74-1, ref. 8m, 13g, 13h; 2g [953-01-5, ref. 8m, 8n, 8q, 13e, 13g; 2h [953-14-0, ref. 8m, 8p, 8q, 13b-d, 13g, 13h; 2i [787-77-9, ref. 8m, 8n, 8p, 13e, 13g, 13h, 13j; 2j [1027-32-3, ref. 13g, 13h, 13j; 2k [1027-40-3, ref. 8m, 13b d. The synthesis and isolation of 2b have been reported by Nölting and Stricker,8c but no data except the melting point were given. Data for 2b: mp 119-121°C (lit.8c mp 120-122°C, IR (film, 3364, 3228, 3008, 1627, 1510, 1463, 1444, 1276, 1240, 1153, 1012, 875, 814 cm-1. 1H NMR 200 MHz, CCl 4
    • +]: 240.1626; found: 240.1622.
  • 61
    • 34447500619 scopus 로고
    • Chem. Abstr. 1965, 62, 7607c.
    • (1965) Chem. Abstr , vol.62
  • 65
    • 34447503963 scopus 로고    scopus 로고
    • Preparation of 2,4,6-Trimethylaniline 2,2′,4,4′,6, 6′-Hexamethylazobenzene (1e, 0.50 g, 1.88 mmol) was added to a mixture of H2O (200 mL, MeOH (200 mL, and CH2Cl 2 (30 mL, The resulting mixture was stirred and heated to reflux, and Na2S2O4 (2.00 g, 11.5 mmol) was added. After stirring at reflux for 3 h, the product mixture was poured into ice and extracted with Et2O (3 x 100 mL, The combined extracts were dried (MgSO4) and filtered, and the solvent was subsequently removed under reduced pressure to give a residue, from which 0.42 g (82, of 2,4,6-trimethylaniline was isolated by flash chromatography silica, hexane-EtOAc in a 90:10 ratio, The spectroscopic and physical properties of the product were identical to those of the aniline derivative used to prepare azobenzene 1e
    • 4) and filtered, and the solvent was subsequently removed under reduced pressure to give a residue, from which 0.42 g (82%) of 2,4,6-trimethylaniline was isolated by flash chromatography (silica, hexane-EtOAc in a 90:10 ratio). The spectroscopic and physical properties of the product were identical to those of the aniline derivative used to prepare azobenzene 1e.
  • 74
    • 34447529386 scopus 로고
    • Reduktion Teil I
    • Kropf, H, Ed, Georg Thieme Verlag: Stuttgart
    • (a) Lehmann, J. Reduktion Teil I In Methoden der Organischen Chemie (Houben-Weyl), Vol. IV/1c; Kropf, H., Ed.; Georg Thieme Verlag: Stuttgart, 1980, 551.
    • (1980) Methoden der Organischen Chemie (Houben-Weyl) , vol.IV 1c , pp. 551
    • Lehmann, J.1
  • 75
    • 34447517676 scopus 로고
    • Reduktion Teil II
    • Kropf, H, Ed, Georg Thieme Verlag: Stuttgart
    • (b) Hajos, A. Reduktion Teil II In Methoden der Organischen Chemie (Houben-Weyl), Vol. IV/1d; Kropf, H., Ed.; Georg Thieme Verlag: Stuttgart, 1981, 365.
    • (1981) Methoden der Organischen Chemie (Houben-Weyl) , vol.IV 1d , pp. 365
    • Hajos, A.1


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.