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A Study on the Synthesis of p-phenylenediamine (PPD) Using Copper Catalyst
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  • Journal title : Korean Chemical Engineering Research
  • Volume 54, Issue 3,  2016, pp.425-430
  • Publisher : The Korean Institute of Chemical Engineers
  • DOI : 10.9713/kcer.2016.54.3.425
 Title & Authors
A Study on the Synthesis of p-phenylenediamine (PPD) Using Copper Catalyst
Kim, Jungsuk; Lee, Sang-yong; Lee, Jungho; Choi, Won Choon; Kang, Na Young; Park, Sunyoung; Kim, Kiwoong; Lim, Jong Sung; Park, Yong-Ki; Seo, Hwimin;
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 Abstract
p-Phenylenediamine (PPD) was synthesized by aromatic amination of p-diiodobenzene (PDIB) using liquid ammonia and Cu-catalysts. The effects of the catalyst, reductant, ammonia quantity and reaction temperature on PPD production were investigated. Cu(I) compounds and Cu powder were selected as catalyst due to a higher selectivity than Cu(II) compounds. As the catalyst quantity increased, rate of PPD production as well as side reaction of aniline decreased with increasing the quantity of ammonia. Reductants such as ascorbic acid, hydrazine and dihydroxyfumaric acid were tested to lower the catalyst loading. The use of reductants resulted in increasing the reaction rate but also increased the amount of aniline The rate of reaction using ascorbic acid or dihydroxyfumaric acid was faster than that using hydrazine. The lowest side reaction of aniline was found in dihydroxyfumaric acid of reductants investigated.
 Keywords
p-phenylenediamine;p-diiodobenzene;copper(I) catalysts;amination;dehalogenation;
 Language
Korean
 Cited by
 References
1.
Stojanovic, D. B., Zrilic, M., Jancic-Heinemann, R., Zivkovic, L., Kojovic, A., Uskokovic, P. S. and Aleksic, R., "Mechanical and Anti-Stabbing Properties of Modified Thermoplastic Polymers Impregnated Multiaxial ${\rho}$-Aramid Fabrics," Polym. Adv. Technol., 24, 772-776(2013). crossref(new window)

2.
Lee, H. J., "Method for the Preparation of p-Phenelynediamine," Korea Patent No. 2014032191(2014).

3.
Smiley, R. A. Phenylene- and Toluenediamines in Ullmann's Encyclopedia of Industrial Chemistry, Wiley-VCH, Weinheim (2002).

4.
Beletskaya, I. P. and Chepracov, A. V., "The Complementary Competitors: Palladium and Copper in C-N Cross-Coupling Reactions," Organometallics, 31, 7753-7808(2012). crossref(new window)

5.
Seo, H. M., Park, Y. K., Song, B. S. and Noh, H. D., "Method for Manufacturing Phenylenediamine Containing Recovery Process of Iodine," Korea Patent No. 10-1482664(2015).

6.
Shimizu, A. and Yamataka, K., "Method for Producing Iodine or Iodine Derivatives," U.S. Patent No. 4487752(1984).

7.
Herkelmann, R., Rudolph, W. and Seffer, D., "Method of Recovering Iodine," U.S. Patent No. 5356611(1994).

8.
Rule, M., Lane, D. W., Larkins, Jr. T. H. and Tustin, G. C., "Process for Preparing Iodinated Aromatic Compounds", U.S. Patent No. 4746758(1988).

9.
Kim, H. S., Cha, I. H. and Lim, J. B., "Method of Preparing Iodinated Aromatic Compounds with High Yield," Korea Patent No. 10-1123148(2012).

10.
Aubin, Y., Fischmeister, C., Thomas, C. M. and Renaud, J.-L., "Direct Amination of Aryl Halides with Ammonia," Chem. Soc. Rev., 39, 4130-4145(2010). crossref(new window)

11.
Xu, H. and Wolf, C., "Efficient Copper-Catalyzed Coupling of Aryl Chlorides, Bromides and Iodides with Aqueous Ammonia," Chem. Commun., 3035-3037(2009).

12.
Wang, D., Qian, A. B., Cai, A. and Ding, K., "An Efficient Copper-Catalyzed Amination of Aryl Halides by Aqueous Ammonia," Adv. Synth. Catal., 351, 1722-1726(2009). crossref(new window)

13.
Xu, H. J., Liang, Y. F., Cai, Z. Y., Qi, H. X., Yang, C. Y. and Feng, Y. S., "CuI-Nanoparticles-Catalyzed Selective Synthesis of Phenols, Anilines, and Thiophenols from Aryl Halides in Aqueous Solution," J. Org. Chem., 76, 2296-2300(2011). crossref(new window)

14.
Ji, P., John, H. A. and Michael, I. P., "Copper(I)-Catalyzed Amination of Aryl Halides in Liquid Ammonia," J. Org. Chem., 77, 7471-7478(2012). crossref(new window)

15.
Mansour, M., Giacovazzi, R., Ouali, A., Taillefer, M. and Jutand, A., "Activation of Aryl Halides by $Cu^0$/1,10-Phenanthroline: $Cu^0$ as Precursor of CuI Catalyst in Cross-Coupling Reactions," Chem. Commun., 6051-6053 (2008).

16.
Cho, H.-K. and Lim, J. S., "Synthesis of ${\rho}$-Phenylenediamine (PPD) Using Supercritical Ammonia," Korean Chem. Eng. Res., 53, 53-56(2015). crossref(new window)

17.
Tye, J. W., Weng, Z., Giri, R. and Hartwig, J. F., "Copper(I) Phenoxide Complexes in the Etherification of Aryl Halides," Angew. Chem. Int. Ed., 49, 2185-2189(2010). crossref(new window)

18.
Fier, P. S., Luo, J. and Hartwig, J. F., "Copper-Mediated Fluorination of Arylboronate Esters. Identification of a Copper(III) Fluoride Complex," J. Am. Chem. Soc., 135, 2552-2559(2013). crossref(new window)