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PROSPEKTING BIOMASSA improving, adding and finding further value of biomass.

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Presentation on theme: "PROSPEKTING BIOMASSA improving, adding and finding further value of biomass."— Presentation transcript:

1 PROSPEKTING BIOMASSA improving, adding and finding further value of biomass

2 STRATEGI Gallezot, P., Conversion of biomass to selected chemical products, Chemical Society Review, 2011, DOI: /c1cs15147a

3 STRATEGI Gallezot, P., Conversion of biomass to selected chemical products, Chemical Society Review, 2011, DOI: /c1cs15147a FUNCTIONAL BIOPOLYMERS

4 Cellulose accessed 4 March 2014

5 Cellulose accessed 4 March 2014

6 Cellulose u/carbs_lipids_proteins/index.htm

7 Cellulose u/carbs_lipids_proteins/index.htm html

8 Synthesis of sulfonated amino-polysaccharides having anti-HIV and blood anticoagulant activities Kazuyuki Hattori, Takashi Yoshida, Hideki Nakashimab, Mariappan Premanathan, Rieko Aragaki, Toru Mimura, Yutaro Kaneko, Naoki Yamamoto, and Toshiyuki Uryu, Carbohydrate Research, 1998, 312, 1-8.

9 Synthesis of sulfonated amino-polysaccharides having anti-HIV and blood anticoagulant activities Kazuyuki Hattori, Takashi Yoshida, Hideki Nakashimab, Mariappan Premanathan, Rieko Aragaki, Toru Mimura, Yutaro Kaneko, Naoki Yamamoto, and Toshiyuki Uryu, Carbohydrate Research, 1998, 312, 1-8.

10 Synthesis of sulfonated amino-polysaccharides having anti-HIV and blood anticoagulant activities Kazuyuki Hattori, Takashi Yoshida, Hideki Nakashimab, Mariappan Premanathan, Rieko Aragaki, Toru Mimura, Yutaro Kaneko, Naoki Yamamoto, and Toshiyuki Uryu, Carbohydrate Research, 1998, 312, 1-8.

11 Synthesis of sulfonated amino-polysaccharides having anti-HIV and blood anticoagulant activities Kazuyuki Hattori, Takashi Yoshida, Hideki Nakashimab, Mariappan Premanathan, Rieko Aragaki, Toru Mimura, Yutaro Kaneko, Naoki Yamamoto, and Toshiyuki Uryu, Carbohydrate Research, 1998, 312, 1-8.

12 Synthesis of sulfonated amino-polysaccharides having anti-HIV and blood anticoagulant activities Kazuyuki Hattori, Takashi Yoshida, Hideki Nakashimab, Mariappan Premanathan, Rieko Aragaki, Toru Mimura, Yutaro Kaneko, Naoki Yamamoto, and Toshiyuki Uryu, Carbohydrate Research, 1998, 312, 1-8.

13 Synthesis of sulfonated amino-polysaccharides having anti-HIV and blood anticoagulant activities Kazuyuki Hattori, Takashi Yoshida, Hideki Nakashimab, Mariappan Premanathan, Rieko Aragaki, Toru Mimura, Yutaro Kaneko, Naoki Yamamoto, and Toshiyuki Uryu, Carbohydrate Research, 1998, 312, 1-8.

14 Synthesis of sulfonated amino-polysaccharides having anti-HIV and blood anticoagulant activities Kazuyuki Hattori, Takashi Yoshida, Hideki Nakashimab, Mariappan Premanathan, Rieko Aragaki, Toru Mimura, Yutaro Kaneko, Naoki Yamamoto, and Toshiyuki Uryu, Carbohydrate Research, 1998, 312, 1-8. Sulfoamido group in the sulfoamido and sulfonate group-containing polysaccharides has anti-HIV activity, but also plays an important role in increasing anticoagulant activity

15 Cellulose sulfuric acid: An efficient biodegradable and recyclable solid acid catalyst for the one-pot synthesis of aryl-14H-dibenzo[a.j]xanthenes under solvent-free conditions Xanthenes and benzoxanthene derivatives posses biological and therapeutic properties, such as antiviral [1], antibacterial [2], anti- inflammatory [3] activities, and photodynamic therapy [4]. J. Venu Madhava, Y. Thirupathi Reddy, P. Narsimha Reddy, M. Nikhil Reddy, Suresh Kuarma, Peter. A. Crooks, B. Rajitha, J. Mol. Cat. A: Chem., 2009, 304,85–87. [1] R.W. Lambert, J.A. Martin, J.H. Merrett, K.E.B. Parkes, G.J. Thomas, Chem Abstr., 1997, 126, y; PCT Int. Appl.WO (1997). [2] T. Hideo, Chem. Abstr.1982, 95, 80922b; Jpn. Tokyo Koho JP, (1981). [3] J.P. Poupelin, G. Saint-Ruf, O. Foussard-Blanpin, G. Narcisse, G. Uchida-Ernouf, R. Lacroix, Eur. J. Med. Chem., 1978, 13, 67. [4] R.M. Ion, Prog. Catal., 1997, 2, 55.

16 J. Venu Madhava, Y. Thirupathi Reddy, P. Narsimha Reddy, M. Nikhil Reddy, Suresh Kuarma, Peter. A. Crooks, B. Rajitha, J. Mol. Cat. A: Chem., 2009, 304,85–87. The synthesis of xanthenes has been improved by condensing -naphthol with aldehydes in the presence of an acid catalyst such as sulfamic acid [17], Amberlyst-15 [18], AcOH-H 2 SO 4 [19], p-TSA [20] and silica sulfuric acid [21]. Some of these methods suffer from severe drawbacks, including use of large amounts of expensive reagents and catalysts, low yield, use of toxic solvents and catalysts, long reaction times, special apparatus, and tedious workup procedures, [17] B. Rajitha, B. Sunil Kumar, Y. Thirupathi Reddy, P. Narsimha Reddy, N. Sreenivasulu, Tetrahedron Lett., 2005, 46, [18] S. Ko, C.F. Yao, Tetrahedron Lett., 2006, 47, [19] R.J. Sarma, J.B. Baruah, Dyes Pigments, 2005, 64, 911. [20] A.R. Khosropour, M.M. Khodaei, H. Moghannian, Synlett., 2005, [21] H.R. Shaterian, M. Ghashang, A. Hassankhani, Dyes Pigments, 2008, 76, 564. Cellulose sulfuric acid: An efficient biodegradable and recyclable solid acid catalyst for the one-pot synthesis of aryl-14H-dibenzo[a.j]xanthenes under solvent-free conditions

17 J. Venu Madhava, Y. Thirupathi Reddy, P. Narsimha Reddy, M. Nikhil Reddy, Suresh Kuarma, Peter. A. Crooks, B. Rajitha, J. Mol. Cat. A: Chem., 2009, 304,85–87. Cellulose sulfuric acid: An efficient biodegradable and recyclable solid acid catalyst for the one-pot synthesis of aryl-14H-dibenzo[a.j]xanthenes under solvent-free conditions

18 J. Venu Madhava, Y. Thirupathi Reddy, P. Narsimha Reddy, M. Nikhil Reddy, Suresh Kuarma, Peter. A. Crooks, B. Rajitha, J. Mol. Cat. A: Chem., 2009, 304,85–87. Cellulose sulfuric acid: An efficient biodegradable and recyclable solid acid catalyst for the one-pot synthesis of aryl-14H-dibenzo[a.j]xanthenes under solvent-free conditions

19 J. Venu Madhava, Y. Thirupathi Reddy, P. Narsimha Reddy, M. Nikhil Reddy, Suresh Kuarma, Peter. A. Crooks, B. Rajitha, J. Mol. Cat. A: Chem., 2009, 304,85–87. Cellulose sulfuric acid: An efficient biodegradable and recyclable solid acid catalyst for the one-pot synthesis of aryl-14H-dibenzo[a.j]xanthenes under solvent-free conditions

20 J. Venu Madhava, Y. Thirupathi Reddy, P. Narsimha Reddy, M. Nikhil Reddy, Suresh Kuarma, Peter. A. Crooks, B. Rajitha, J. Mol. Cat. A: Chem., 2009, 304,85–87. Cellulose sulfuric acid: An efficient biodegradable and recyclable solid acid catalyst for the one-pot synthesis of aryl-14H-dibenzo[a.j]xanthenes under solvent-free conditions

21 Sulfonated cellulose and starch: New biodegradable and renewable solid acid catalysts for efficient synthesis of quinolines Ahmad Shaabani, Abbas Rahmati, and Zahra Badri, Cat. Commun., 2008, 9, A typical procedure to prepare quinoline apply catalyst strong protic inorganic liquid acids such as HCl, H 2 SO 4, and polyphosphoric acid [8], Lewis acids such as ZnCl 2, NaAuCl 6, and AuCl 3.3H 2 O [9], and transition- metals such as ruthenium and palladium [10]. [8] A. Arcadi, M. Chiarini, S.D. Giuseppe, F. Marinelli, Synlett., 2003, 203. [9] (a) B.R. McNaughton, B.L. Miller, Org. Lett., 2003, 5, 4257; (b) A. Walser, T. Flyll, R.I. Fryer, J. Heterocycl. Chem., 1975, 12, 737. [10] (a) L.S. Hegedus, Angew. Chem. Int. Ed., 1988, 27, 1113; (b) Y. Watanabe, Y. Tsuji, Y. Ohsugi, Tetrahedron Lett., 1981, 22, 2667; (c) Y. Watanabe, N. Suzuki, Y. Tsuji, S.C. Shim, T. Mitsudo, Bull. Chem. Soc. Jpn., 1984, 57, 435; (d) Y. Watanabe, K. Takatsuki, S.C. Shim, T. Mitsudo, Y. Takegami, Bull. Chem. Soc. Jpn., 1978, 51, 3397.

22 Sulfonated cellulose and starch: New biodegradable and renewable solid acid catalysts for efficient synthesis of quinolines Ahmad Shaabani, Abbas Rahmati, and Zahra Badri, Cat. Commun., 2008, 9, Catalyst preparation: To a magnetically stirred mixture of cellulose (5.00 g) or starch (5.00 g) in CHCl 3 (20 ml), chlorosulfonic acid (1.00 g, 9 mmol) was added dropwise at 0 o C during 2 h. After addition was complete, the mixture was stirred for 2 h until HCl was removed from reaction vessel. Then, the mixture was filtered and washed with methanol (30 ml) and dried at room temperature to obtain cellulose sulfuric acid as white powder (5.22 g) or starch sulfuric acid as cream powder (5.06 g). Sulfur content was analyzed by conventional elemental analysis, was 0.55 and 0.12 mmol/g for cellulose sulfuric acid and starch sulfuric acid, respectively. The number of H + site of cellulose-SO 3 H and starch-SO 3 H was determined by acid–base titration was 0.50 and 0.10 meq/g, respectively. This value corresponds to about 90% and 83% of the sulfur content, indicating that most of the sulfur species on both of the samples are in the form of the sulfonic acid groups.

23 Sulfonated cellulose and starch: New biodegradable and renewable solid acid catalysts for efficient synthesis of quinolines Ahmad Shaabani, Abbas Rahmati, and Zahra Badri, Cat. Commun., 2008, 9, 13-16

24 Sulfonated cellulose and starch: New biodegradable and renewable solid acid catalysts for efficient synthesis of quinolines Ahmad Shaabani, Abbas Rahmati, and Zahra Badri, Cat. Commun., 2008, 9, 13-16

25 Solvent-free synthesis of  -aminophosphonates: Cellulose-SO 3 H as an efficient catalyst Krishnammagari Suresh Kumar, Balam Satheesh Krishna, Chinnapareddy Bhupendra Reddy, Mudumala Veera Narayana Reddy, Cirandur Suresh Reddy, Arabian Journal of Chemistry. 2012,  -Aminophosphonates and derivatives has many potential bioactivities: Antibiotics 1 ; herbicides, fungicides, insecticides 2 enzyme inhibitors 3 HIV protease 4 plant growth regulators 5 anti-thrombotic agents 6 peptidases and proteases 7 1.Atherton, F.R., Hassal, C.H., Lambert, R.W., J. Med. Chem., 1986, 29, 29–40. 2.Maier, L., Spoerri, H., Organic phosphorus compounds. Resolution of 1-amino-2-(4-fluorophenyl)ethylphosphonic acid as well as some di- and tripeptides. Phosphorus, Sulfur Silicon Relat. Elem., 1991, 61, 69–75. 3.Allen, M.C., Fuhrer, W., Tuck, B., Wade, R., Wood, J.M., J. Med. Chem., 1989, 32, 1652– Peyman, A., Stahl, W., Wagner, K., Ruppert, D., Budt, K.H., Non-peptide-based inhibitors of human immunodeficiency virus-1 protease. Bioorg. Med. Chem. Lett., 1994, 4, 2601– Emsley, J., Hall, D., The Chemistry of Phosphorous. Harper and Row, London. 6.Meyer, J.H., Barlett, P.A., J. Am. Chem. Soc., 1998, 120, 4600– Miller, D.J., Hammond, S.M., Anderluzzi, D., Bugg, T.D.H., Aminoalkylphosphinate inhibitors of D-ala-D-ala adding enzyme. J. Chem. Soc., Perkin Trans., 1998, 1, 131–142.

26 Krishnammagari Suresh Kumar, Balam Satheesh Krishna, Chinnapareddy Bhupendra Reddy, Mudumala Veera Narayana Reddy, Cirandur Suresh Reddy, Arabian Journal of Chemistry. 2012, Solvent-free synthesis of a-aminophosphonates: Cellulose-SO 3 H as an efficient catalyst

27 Solvent-free synthesis of  -aminophosphonates: Cellulose-SO 3 H as an efficient catalyst Krishnammagari Suresh Kumar, Balam Satheesh Krishna, Chinnapareddy Bhupendra Reddy, Mudumala Veera Narayana Reddy, Cirandur Suresh Reddy, Arabian Journal of Chemistry. 2012, Solvent-free synthesis of  -aminophosphonates: Cellulose-SO 3 H as an efficient catalyst

28 Krishnammagari Suresh Kumar, Balam Satheesh Krishna, Chinnapareddy Bhupendra Reddy, Mudumala Veera Narayana Reddy, Cirandur Suresh Reddy, Arabian Journal of Chemistry. 2012, Solvent-free synthesis of  -aminophosphonates: Cellulose-SO 3 H as an efficient catalyst

29 Krishnammagari Suresh Kumar, Balam Satheesh Krishna, Chinnapareddy Bhupendra Reddy, Mudumala Veera Narayana Reddy, Cirandur Suresh Reddy, Arabian Journal of Chemistry. 2012, Solvent-free synthesis of  -aminophosphonates: Cellulose-SO 3 H as an efficient catalyst

30 Javad Safari, Sayed Hossein Banitaba, Shiva D. Khalili, Journal of Molecular Catalysis A: Chemical, 2011, 335, 46–50 Cellulose sulfuric acid catalyzed multicomponent reaction for efficient synthesis of 1,4-dihydropyridines via unsymmetrical Hantzsch reaction in aqueous media 1,4-Dihydropyridines (1,4-DHPs) are important class of compounds in the field of drugs and pharmaceuticals [9]. The DHP moiety is common to numerous bioactive compounds which include various antihypertensive, vasodilator, antimutagenic, antitumor and antidiabetic agents [10–13]. 1,4-DHPs are generally synthesised by classical Hantzsch method, which involves cyclocondensation of an aldehyde, -ketoesters and ammonia either in acetic acid or in refluxing ethanol for long reaction times which typically leads to low yields [14–16]. [10] R.A. Janis, D.A. Triggle, J. Med. Chem., 1983, 25, 775–779. [11] R.H. Bocker, F.P. Guengerich, J. Med. Chem., 1986, 28, 1596–1601. [12] A.C. Gaudio, A. Korolkovas, Y. Tkahata, J. Pharm. Sci., 1994, 83, 1110–1114. [13] M.F. Gordeev, D.V. Patel, E.M. Gordon, J. Org. Chem., 1996, –927. [14] A. Dondoni, A. Massi, E. Minghini, V. Bertolasi, Tetrahedron, 2004, 60, 2311–2314. [15] A. Hantzsch, Ber. Dtsch. Chem. Ges., 1881, 14, 1637–1640. [16] B. Love, K.M. Sander, J. Org. Chem., 1965, 30, 1914–1919.

31 Javad Safari, Sayed Hossein Banitaba, Shiva D. Khalili, Journal of Molecular Catalysis A: Chemical, 2011, 335, 46–50 Cellulose sulfuric acid catalyzed multicomponent reaction for efficient synthesis of 1,4-dihydropyridines via unsymmetrical Hantzsch reaction in aqueous media Preparation of cellulose sulfuric acid To a magnetically stirred mixture of 5.0 g of cellulose in 20 ml of n-hexane, 1.0 g of chlorosulfonic acid (9 mmol) was added drop wise at 0 o C during 2 h. HCl gas was removed from the reaction vessel immediately. After the addition was complete, the mixture was stirred for 2 h. Then the mixture was filtered and washed with 30 ml of acetonitrile and dried at room temperature to afford 5.25 g of cellulose sulfuric acid as a white powder. Sulfur content of the samples by conventional elemental analysis, was 0.55 for cellulose sulfuric acid. The number of H + sites on the cellulose-SO 3 H was determined by acid–base titration was 0.50 mequiv./g [31]. [31] S. Ahmad, M. Ali, Appl. Catal. A: Gen., 2007, 331, 149–153.

32 Javad Safari, Sayed Hossein Banitaba, Shiva D. Khalili, Journal of Molecular Catalysis A: Chemical, 2011, 335, 46–50 Cellulose sulfuric acid catalyzed multicomponent reaction for efficient synthesis of 1,4-dihydropyridines via unsymmetrical Hantzsch reaction in aqueous media

33 Javad Safari, Sayed Hossein Banitaba, Shiva D. Khalili, Journal of Molecular Catalysis A: Chemical, 2011, 335, 46–50 Cellulose sulfuric acid catalyzed multicomponent reaction for efficient synthesis of 1,4-dihydropyridines via unsymmetrical Hantzsch reaction in aqueous media Solvent effect

34 Enantioseparation: Synthesis and characterization of camphorsulfonyl acetate of cellulose Dingshu Xiao Jiwen Hu, Mingqiu Zhang, Mingwei Li, Guozhi Wang and Haisong Yao, Carbohydrate Research, 2004, 339, 1925–1931 (1R)-(+)-camphor-10-sulfonic acid (HCSA) has acted as chiral resolution agent in crystallization and chromatography 6 and the camphor structure proves to be a very useful chiral probe in HPLC, NMR and X-ray crystallographic determination of absolute configuration Klaus, S.; Matthias, K.; Karlheinz, D. Tetrahedron: Asymmetry, 1997, 8(7), 979– Harada, N.; Soutome, T.; Murai, S.; Uda, H. Tetrahedron: Asymmetry, 1993, 4(8), 1755–1758.

35 Enantioseparation: Synthesis and characterization of camphorsulfonyl acetate of cellulose Dingshu Xiao Jiwen Hu, Mingqiu Zhang, Mingwei Li, Guozhi Wang and Haisong Yao, Carbohydrate Research, 2004, 339, 1925– Synthesis of (1R)-(+)-camphor-10-sulfonyl chloride (CSC) (1R)-(+)-camphor-10-sulfonyl chloride (CSC) acting as the chiral auxiliary was prepared from (1R)-(+)-camphor-10-sulfonic acid (HCSA).16 SOCl2 (70 mL, 962 mmol) was dripped into HCSA (50 g, 217 mmol) at 0 C. The mixture was stirred for 30 min at 0 C and then heated to 40–50 C for 2 h. SOCl2 was removed via reduced pressure distillation. The crude material, followed by repeated recrystallization in ligroin, then dried under vacuum, gave the desired product (56 g, 98%), colourless, mp 65–66 o C Chemical modification of CA with CSC CSC solution (3 g, 11 mmol of CSC dissolved in 20mL acetone) was dripped to CA solution (5 g, 19 mmol of CA dissolved in 50mL dry acetone) in ice-bath accompanied by stirring and nitrogen protection. The CA solution containing 4-dimethylaminopyridine (0.025 g) as the catalyst and Et 3 N (1.5 mL, 11 mmol) was stirred at 0–5 C for 3 h, and then at room temperature for 2 days. Eventually, it was poured into MeOH. The white precipitate was collected and purified by repeatedly washing. Further purification of the product was performed by Soxhlet extraction with MeOH for the first 2 h, after which the solvent was changed for fresh one and the extraction was conducted for the additional 24 h. Then the end product was dried under vacuum at 85 C and stored in desiccators. Yield: 7.29 g, 99.2%.

36 Enantioseparation: Synthesis and characterization of camphorsulfonyl acetate of cellulose Dingshu Xiao Jiwen Hu, Mingqiu Zhang, Mingwei Li, Guozhi Wang and Haisong Yao, Carbohydrate Research, 2004, 339, 1925–1931 DS CS was determined by chemical analysis method. 17 Sample (0.3 g) was added to a flask containing 75% aqueous alcohol solution (40 mL) and then heated to 60 o C for 30 min. Afterwards, 40 mL of 0.5M NaOH aqueous solution was added, and was further heated for additional 15 min. Finally, the sample was cooled to room temperature and titrated with 0.5M NaOH after 72 h. After 10 h the solution was back-titrated with 0.5M HCl. Phenolphthalein was used as the indicator. The DSCS values of the samples were deduced from the following formula: D and B is mL of HCl and NaOH solutions consumed for titration of blank. C and A is mL of HCl and NaOH solutions consumed for titration of the sample. W means grams of the sample. DS AC 2.42 representing the total degree of substitution of acetyl group in the sample.

37 Enantioseparation: Synthesis and characterization of camphorsulfonyl acetate of cellulose Dingshu Xiao Jiwen Hu, Mingqiu Zhang, Mingwei Li, Guozhi Wang and Haisong Yao, Carbohydrate Research, 2004, 339, 1925–1931

38 Enantioseparation: Synthesis and characterization of camphorsulfonyl acetate of cellulose Dingshu Xiao Jiwen Hu, Mingqiu Zhang, Mingwei Li, Guozhi Wang and Haisong Yao, Carbohydrate Research, 2004, 339, 1925–1931

39 Catalyst bring reaction not only faster, it bring IT life


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