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 Pharmaceutical Intermediates
Cytec offers a variety of products which, in the hands of the pharmaceutical synthetic chemist, open opportunities to manipulate the final structure and impart functionality to the API. Phosphonates such as DECMP and TMPA are synthetic reagents used in Horner Emmons Wadsworth (HEW) chemistry to build the final API structure. DECMP initially leaves the cyanoethylene fragment which can be further transformed to an amine, amide, triazole, tetrazole etc. The possibilities are endless under the direction of the experienced synthetic chemist. TIPMDP, a commercial bisphosphonate, is a major building block for a number of launched drugs for combating bone diseases. The acidic protons on the central methylene carbon are easily extracted under very mild conditions and the resultant anion is available for reaction with electrophilic substrates.
Phosphorylation with chlorophosphates, phosphite/phosphates and phosphonates are common within the fine chemical and pharmaceutical industries. Phosphorylation is an approach often employed in the production of pro-drugs or to increase the aqueous solubility and oral bio-availability of the final drug. The phosphorus esters can be tailored to the application to insure compatibility with functionality elsewhere in the molecule and include the linear and branched alkyl, benzyl and aromatic esters. A number of customer specific phosphonate and phosphate phosphorylating agents are being developed. Cytec welcomes the opportunity to discuss your needs and to work closely together to develop mutually beneficial solutions fitting your specific requirements.
| Pharmaceutical Intermediate Product Information |
| Product Name |
Chemical Name |
Format |
| TIPMDP |
tetraisopropyl methylenediphosphonate |
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| DECMP |
diethyl cyanomethylphosphonate |
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| TMPA |
trimethyl phosphonoacetate |
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| DPCP |
diphenyl chlorophosphate |
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| DECP |
diethyl chlorophosphate |
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| EDPP |
ethyl diphenylphosphonate |
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| DPPC |
diphenylphosphinic chloride |
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| Pharmaceutical Intermediates Technical References |
| Category |
Journal |
Title |
Author |
| Desulferization |
US 5509945; Iowa State University Research Foundation, Inc., USA |
Mild desulfurization of sulfur-bearing materials |
Verkade, John G.; Mohan, Thyagarajan |
| US 5437696; Iowa State University Research Foundation, Inc., USA |
Mild desulfurization of sulfur-bearing materials |
Verkade, John G.; Mohan, Thyagarajan |
| Energy Fuels (1995), 9(2), 354-8 |
31P Solid-State NMR Study of Coals Derivatized with Phosphorus Reagents |
Erdmann, K.; Mohan, T.; Verkade, J. G. |
| Solvents |
Chemical Physical Letters, (2003), 381, 278-286 |
Solvent dynamics of coumarin 153 in several classes of ionic liquids: cation dependence of the ultrafast component |
Arzhantsez, S.; Ito, N.; Heitz, M. and Maroncelli, M. |
| Suzuki Coupling |
Chem. Commun., (2002), 1986-1987 |
Suzuki cross-coupling reactions of aryl halides in phosphonium salt ionic liquid under mild conditions |
McNulty,J.; Capretta, A.; Wilson, J.; Dyck, J.; Adabeng,G. and Robertson, A. |
| J. Org. Chem., (2004),69,5082-5086 |
Palladium Complexes of 1,3,5,7-
Tetramethyl-2,4,8-trioxa-6-phenyl-6-
phosphaadamantane: Synthesis, Chrystal Structure and Use in Suzuki and Sonogashira Reactions and the a-Arylation of Ketones |
Adjabeng, G.; Brenstrum,T.; Frampton,C.; Robertson, A.; Hillhouse, J. H.; McNulty, J and Capretta, A. |
| Organic Letters, (2003), 5, 953-955 |
Novel class or tertiary phosphine ligands based on a phospha-adamantane framework and use in the Suzuki cross-coupling reactions of aryl halides under mild conditions |
Adjabeng, G.; Brenstrum,T.;Wilson, J; Frampton,C.; Robertson, A.; Hillhouse, J. H.; McNulty, J and Capretta, A. |
| Heck Coupling |
Tetrahedron Letters, (2004),45(41), 7629-7631 |
Heck reactions of aryl halides in phosphonium salt ionic liquids. Library screening and applications. |
Gerritismas, D.;Robertson, A.; McNulty, J.; Capretta, A. |
| Condensation Reactions |
Angew. Chem. Int. Ed., (2003), 42, 4051-4054 |
The Role of Acloxyphosphonium Ions and the Stereochemical Influence of Base in the Phosphorane-Mediated Esterification of Alcohols |
McNulty, J.; Capretta, A.; Laritchev, V.; Dyck, J. and Robertson, A. |
| Pure and Appl. Chem.,(1999), 71-6, 1053-1057 |
New Mitsunobu reagents in the C-C bond formation. Application to neutral product synthesis |
Ito, S. and Tsunoda, T. |
| Synlett., (2002), 11, 1901-1903 |
Selective N1-Alkalation of 3,4-Dihydropyrimidin-2(1H)-ones Using Mitsunobu-Type Conditions |
Dallinger, D and Kappe, C. O. |
| Journal of Organic Chemistry (2003), 68(4), 1597-1600 |
Dimethylmalonyltrialkylphosphoranes: New General Reagents for Esterification Reactions Allowing Controlled Inversion or Retention of Configuration on Chiral Alcohols |
McNulty, James; Capretta, Alfredo; Laritchev, Vladimir; Dyck, Jeff; Robertson, Al J. |
| Eu. J. Org. Chem., (2004), 2763-2772 |
Recent Advances in the Mitsunobu Reaction: Modified Reagents and the Quest for Chromatography-Free Separation |
Dembinski,R |
| Peptide Synthesis |
Chemica Oggi (2004),July/Aug.,26 |
Application of tertiary phosphines in peptide chemistry |
Mizhirtitskii,M.; Srpernat, Y.; Robertson,A |
| Phase Transfer Catalysts |
J. Am. Chem. Soc. (1973), 95:11, 3613 |
Phase-Transfer Catalysis. II. Kinetic Details of Cyanide Displacement on 1-Halooctanes |
Starks, C. M.; Owens, R. M. |
| J. Org. Chem., (19821,47,2264-2268 |
Nonhydrated Anion Transfer from the Aqueous to Organic Phase: Enhancement of Nucleophilic Reactivity in Phase-Transfer Catalysis |
Landini, D.; Maia, A. and Podda, G |
| J. Am. Chem. Soc.,(1970),93,195-199 |
Phase-Transfer Catalysis. I. Heterogeneous Reactions Involving Anion Transfer ny Quaternary Ammonium and Phosphonium Salts |
Starks, C. |
| J. Org. Chem.,(1986), 51, 3187-3191 |
Stability of Quaternary Onium Salts under Phase-Transfer Conditions in the Presence of Aqueous Alkaline Solutions |
Landini, D., Maia, A. and Rampoldi, A. |
| J. Am. Chem. Soc., (1975), 97,2345-2349 |
Phase Transfer Catalysis. An Evaluation of Catalysts |
Herriott, A ans Picker, D. |
| J. Am. Chem. Soc. (1981), 103, 3821-3828 |
Mechanism of Polymer-Supported Catalysis. I. Reaction of 1-Bromooctane with Aqueous Sodium Cyanide Catalyzed by Polystyrene-Bound Benzyltri-n-butylphosphonium Ion |
Tomoi, M.; Ford, W. T. |
| Di Sulphide Reduction |
US 6162913; Bristol-Myers Squibb Co., USA |
Preparation of
[4S-(4<SYM97>,7<SYM97>,
10a<SYM98>)
]-4-aminooctahydro-5-oxo-7H-pyrido[2,1-b][1,3]
thiazepine-7-
carboxylic acid methyl ester and its salts via novel disulfides |
Moniot, J. L.; Srivastava, S. K.; Winter, W. J.; Venit, J. J.; Swaminathan, S.; Ramig, K.; Jass, P. A.; Schwinden, M.D.; Dillon, J. L.; Racha, S.; Simpson, J.; Chen, C. and Pack, S. K. |
| Clinical Chemistry, (2001),47, 1821-1828 |
Measurement of Homocysteine and Other Aminothiols in Plasma: Advantages of Using Tris(2-carboxyethyl)phosphine as Reductant Compared with Tri-n-butylphosphine |
Krijt, J.; Vackova, M. and Kozich, V. |
| Balis-Hilman Reaction |
Journal of Organic Chemistry (2003), 68(16), 6463-6465 |
A Phosphine-Catalyzed [3+2] Cycloaddition Strategy Leading to the First Total Synthesis of (-)-Hinesol |
Du, Yishu; Lu, Xiyan |
| Henry Reaction |
Letters in Organic Chemistry, (2004),1,137-139 |
Phosphonium Salt Catalyzed Henry Nitroaldol Reactions |
McNulty, J.; Dyck, J.; Larichev, V.; Capretta, A. and Robertson,A. |
| Hydroformylation |
Dalton (2003),2036-2042 |
Bicyclic phosphines as ligands for cobalt-catalysed hydroformylation |
Crause,C.; Bennie, L.; Damoense, L.; Dwyer, C.; Grove, C.;Grimmer, N.; Rensburg, W.; Kirk, M. M.; Mokheseng, S O. and Stynberg, P |
| Aza-Wittig Reaction |
J. Am. Chem. Soc. (1994), 116, 11143-11144 |
Stereoselective Total Synthesis of Amauromine and 5-N-Acetylardeemin. A Concise Route to the Family of "Reverse-Prenylated" Hexahydropyrroloindole Alkaloids |
Marsden, S. J.; Depew, K.M. and Danishefsky |
| J. Am. Chem. Soc. (1998), 120, 6417-6418 |
Total Synthesis of (-)-Asperlicin and (-)-Asperlicin C |
He,F.; Foxman, B. M. and Snider, B. B. |
| Wittig Reagents |
J. Org. Chem., (1987), 52, 2629-2631 |
The Stereoselective Synthesis of Acyclic and Exocyclic Trisubstituted Olefins via a Hydroxyl-Directed Wittig Reaction |
Lomas, J.S. |
| J. Org. Chem., (2004), 69, 689-694 |
Formation pf P-Ylide under Neutral and Metal-Free Conditions: Transformation of Aziridines and Epoxides to Conjugated Dienes in the Presence of Phosphine |
Fan, R.; Hou, X and Dal, L. |
| Organic Letters, (2001), 3-22, 3591-3593 |
Improved E-Selectivity in the Wittig Reaction of Stabilized Ylides with a-Alkoxyaldehydes and Sugar Lactols |
Harcken, C. and Martin, F. |
| Chemistry--A European Journal (2003), 9(5), 1129-1136 |
The total synthesis of (-)-callystatin A |
Kalesse, Markus; Chary, Khandavalli P.; Quitschalle, Monika; Burzlaff, Arne; Kasper,Cornelia; Scheper, Thomas |
| Staudinger Reaction |
J. Org. Chem. (2000), 65, 5249-5252 |
Synthesis of C-Terminal Glycopeptides from Resin-Bound Glycosyl Azides via a Modified Stauginger Reaction |
Malkinson, J. P.; Falconer, R. A. and Toth, I. |
| J. Org. Chem., (2003), 68, 6463-6465 |
A Phosphine-Catalyzed [3+2] Cycloaddition Strategy Leading to the First Total Synthesis of (-) Hinesol |
Du, Y. and Lu, X. |
| US 6462226; F. Hoffmann-La Roche A.-G., Switz. |
Phosphine chemoselective reduction of azides into 4,5-diaminoshikimic acid derivatives in the presence of catalytic amounts of acids |
Mair, Hans-Juergen |
| J. Am. Chem. Soc., (1997), 119,681-690 |
Influenza Neuraminidase Inhibititors Posessing a Novel Hydrophobic Interaction in the Enzime Active Site: Design, Synthesis and Analysis of Carbocyclic Sialic Acid Analogues with Potent Anti-Influenza Activity |
Kim C U; Lew W; Williams M; Liu H; Zhang L; Swaminathan S; Bischofberger N; Chen M; Mendel D; Tai C; Laver W and Stevens R |
| US 6,462,226; F. Hoffmann-La Roche A.-G., Switz. |
Process for the preparation of 4-5-diamino shikimic acid derivatives |
Mair, Hans-Juergen |
| Setter Reaction |
Tetrahedron Letters, (2003), 44, 1247-1251 |
Tributylphosphine-catalyzed Setter reaction of N,N-dimethylacrylamide: synthesis of N,N-dimethyl-3-aroylpropionamides |
Gong, J. H.; Im, Y. J; Lee, K. Y. and Kim, J. N |
| Michael Reaction |
Tetrahedron Letters, (2002), 43, 8707-8710 |
Tandem Michael/Michael reactions mediated by phosphines or aryl thiolates |
Brown, P. M.; Kappel, N. and Murrphy, P. J. |
| Biocides |
Antimicrobial Agents and Chemotherepy (1994), 38-5, 945-952 |
Synthesis and Antimicrobial Activity of Dimethyl- and trimethyl-Substituted Phosphonium Salts with Alkyl Chains of Various Lengths |
Kanazawa, A.; Ikeda, T. and Endo, T. |
| GB 2145708, Albright and Wilson Ltd., UK |
Biocidal water treatment |
Davis, Keith Philip; Talbot, Robert Eric |
| Liquid Crystals |
J. Am. Chem. Soc. (2000), 122, 3053-3062) |
Smectic Liquid-Crystalline Phases of Quaternary Group VA (Especially Phosphoniul) Salts with Three Equivalent Long n-Alkyl Chains. How Do Layered Assemblies Form in Liquid-Crystalline and Crystalline Phases? |
Abdallah, D. J.; Robertson, A.; Hsu, H. and Weiss,R.G. |
| Phosphine-Porane Complexes |
Tetrahedron Letters, (2004), 45, 407-409 |
A highly efficient general synthesis of phosphine-borane complexes |
McNulty, J. and Zhou, Y. |
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