PROSPEKTING BIOMASSA
improving, adding and finding
further value of biomass
STRATEGI
Gallezot, P., Conversion of biomass to selected chemical products, Chemical Society Review, 2011,
DOI: 10.1039/c1cs15147a
STRATEGI
FUNCTIONAL BIOPOLYMERS
Gallezot, P., Conversion of biomass to selected chemical products, Chemical Society Review, 2011,
DOI: 10.1039/c1cs15147a
Cellulose
http://www.biofuels.apec.org/me_indonesia.html accessed 4 March 2014
Cellulose
http://www.biofuels.apec.org/me_indonesia.html accessed 4 March 2014
Cellulose
http://www.tokresource.org/tok_classes/biobiobio/biomen
u/carbs_lipids_proteins/index.htm
http://polysac3db.cermav.cnrs.fr/discover_cellulose.html
Cellulose
http://www.tokresource.org/tok_classes/biobiobio/biomen
u/carbs_lipids_proteins/index.htm
http://www.elmhurst.edu/~chm/vchembook/547cellulose.
html
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.
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.
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.
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.
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.
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.
Synthesis of sulfonated amino-polysaccharides
having anti-HIV and blood anticoagulant activities
•
Sulfoamido group in the sulfoamido and sulfonate group-containing
polysaccharides has anti-HIV activity, but also plays an important role in
increasing anticoagulant activity
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.
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], antiinflammatory [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, 212377y; PCT Int.
Appl.WO 9706178 (1997).
[2] T. Hideo, Chem. Abstr.1982, 95, 80922b; Jpn. Tokyo Koho JP, 56005480 (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.
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
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-H2SO4 [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, 8691.
[18] S. Ko, C.F. Yao, Tetrahedron Lett., 2006, 47, 8827.
[19] R.J. Sarma, J.B. Baruah, Dyes Pigments, 2005, 64, 911.
[20] A.R. Khosropour, M.M. Khodaei, H. Moghannian, Synlett., 2005, 95510.
[21] H.R. Shaterian, M. Ghashang, A. Hassankhani, Dyes Pigments, 2008, 76, 564.
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
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
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
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
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.
Sulfonated cellulose and starch: New biodegradable and
renewable solid acid catalysts for efficient synthesis of
quinolines
A typical procedure to prepare quinoline apply catalyst strong protic
inorganic liquid acids such as HCl, H2SO4, and polyphosphoric acid [8],
Lewis acids such as ZnCl2, NaAuCl6, and AuCl3.3H2O [9], and transitionmetals 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.
Ahmad Shaabani, Abbas Rahmati, and Zahra Badri, Cat. Commun., 2008, 9, 13-16
Sulfonated cellulose and starch: New biodegradable and
renewable solid acid catalysts for efficient synthesis of
quinolines
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 oC 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-SO3H and starch-SO3H 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.
Ahmad Shaabani, Abbas Rahmati, and Zahra Badri, Cat. Commun., 2008, 9, 13-16
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
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
Solvent-free synthesis of a-aminophosphonates:
Cellulose-SO3H as an efficient catalyst
a-Aminophosphonates and derivatives has many potential
bioactivities:
•
•
•
•
•
•
•
1.
2.
Antibiotics1;
herbicides, fungicides, insecticides2
enzyme inhibitors3
HIV protease4
plant growth regulators5
anti-thrombotic agents6
peptidases and proteases7
Atherton, F.R., Hassal, C.H., Lambert, R.W., J. Med. Chem., 1986, 29, 29–40.
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, 1652–1661.
4. 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, 2601–2604.
5. Emsley, J., Hall, D., 1976. The Chemistry of Phosphorous. Harper and Row, London.
6. Meyer, J.H., Barlett, P.A., J. Am. Chem. Soc., 1998, 120, 4600–4609.
7. 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.
Krishnammagari Suresh Kumar, Balam Satheesh Krishna, Chinnapareddy Bhupendra Reddy, Mudumala Veera Narayana
Reddy, Cirandur Suresh Reddy, Arabian Journal of Chemistry. 2012, http://dx.doi.org/10.1016/j.arabjc.2012.09.009
Solvent-free synthesis of a-aminophosphonates:
Cellulose-SO3H 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, http://dx.doi.org/10.1016/j.arabjc.2012.09.009
Solvent-free
synthesis
of a-aminophosphonates:
Solvent-free
synthesis
of a-aminophosphonates:
Cellulose-SO
catalyst
3H as an efficient
Cellulose-SO
3H 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, http://dx.doi.org/10.1016/j.arabjc.2012.09.009
Solvent-free
synthesis
of a-aminophosphonates:
Solvent-free
synthesis
of a-aminophosphonates:
Cellulose-SO
catalyst
3H as an efficient
Cellulose-SO
3H 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, http://dx.doi.org/10.1016/j.arabjc.2012.09.009
Solvent-free
synthesis
of a-aminophosphonates:
Solvent-free
synthesis
of a-aminophosphonates:
Cellulose-SO
catalyst
3H as an efficient
Cellulose-SO
3H 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, http://dx.doi.org/10.1016/j.arabjc.2012.09.009
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, 61 924–927.
[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.
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 oC 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-SO3H
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.
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
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
Javad Safari, Sayed Hossein Banitaba, Shiva D. Khalili, Journal of Molecular Catalysis A: Chemical, 2011, 335, 46–50
Enantioseparation: Synthesis and characterization of
camphorsulfonyl acetate of cellulose
• (1R)-(+)-camphor-10-sulfonic acid (HCSA) has acted as chiral
resolution agent in crystallization and chromatography6 and the
camphor structure proves to be a very useful chiral probe in HPLC,
NMR and X-ray crystallographic determination of absolute
configuration7.
6. Klaus, S.; Matthias, K.; Karlheinz, D. Tetrahedron: Asymmetry, 1997, 8(7), 979–982.
7. Harada, N.; Soutome, T.; Murai, S.; Uda, H. Tetrahedron: Asymmetry, 1993, 4(8), 1755–1758.
Dingshu Xiao Jiwen Hu, Mingqiu Zhang, Mingwei Li, Guozhi Wang and Haisong Yao, Carbohydrate Research, 2004, 339,
1925–1931
Enantioseparation: Synthesis and characterization of
camphorsulfonyl acetate of cellulose
3.1. 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 oC.
3.2. 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 Et3N (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%.
Dingshu Xiao Jiwen Hu, Mingqiu Zhang, Mingwei Li, Guozhi Wang and Haisong Yao, Carbohydrate Research, 2004, 339,
1925–1931
Enantioseparation: Synthesis and characterization of
camphorsulfonyl acetate of cellulose
DSCS 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 oC 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. DSAC 2.42
representing the total degree of substitution of acetyl group in the sample.
Dingshu Xiao Jiwen Hu, Mingqiu Zhang, Mingwei Li, Guozhi Wang and Haisong Yao, Carbohydrate Research, 2004, 339,
1925–1931
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
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
Catalyst bring reaction not only
faster, it bring IT life