Dow Haltermann Custom Processing The World of Hydrogen Cyanide Chemistry

Transcription

1 Dow altermann Custom Processing The World of ydrogen Cyanide Chemistry Sharing Your Vision esourcing Your Success

2 Specialists in ydrogen Cyanide Chemistry With Dow s acquisition of the ampshire Chemical Corporation in 1998, and the subsequent formation of Dow altermann Custom Processing, you now have access to over 40 years of experience in hydrogen cyanide chemistry and a worldwide leadership position in custom manufacturing and toll synthesis projects. Dow altermann Custom Processing serves the diverse needs of the pharmaceutical, agrochemical, water treatment, polymer, and photographic industries with an extensive family of intermediates and derivatives based on chemistry. Dow altermann Custom Processing has the unique ability to handle both liquid and sodium cyanide. This unique flexibility is not offered by most custom manufacturers who provide cyanation capabilities. With the ability to handle both and sodium cyanide, we can manufacture a variety of intermediates in both aqueous and non-aqueous reaction systems. Liquid is a unique and versatile building block that often leads to simplified reaction pathways and high purity products that require less purification and minimizes the need to remove salt by-products. The production of chiral intermediates and products is becoming increasingly more important in today s society, especially in the pharmaceutical and agricultural markets. Liquid can be used, with a variety of enzymes, at moderate ps, to produce novel chiral molecules. hydantoins -amino acids cyanohydrins Dow altermann Custom Processing -keto acids amino nitriles Sharing Your Vision... esourcing Your Success -hydroxy acids nitriles amino nitriles Dow altermann Custom Processing, a business unit of The Dow Chemical Company, is exclusively dedicated to providing world-class product and process development and contract manufacturing services to the specialty and fine chemicals industries. Key processes include distillation, batch and continuous fractionation, advanced separations, batch reactions, continuous reactions, and multi-step organic chemistry. Markets served include household and personal care products, electronics, agricultural chemicals, petrochemicals, mining, photographic chemicals, flavors and fragrances, coatings, textiles, and oleochemicals. To learn more, visit 2

3 Look to Dow altermann Custom Processing for these Toll Synthesis and Custom Manufacturing Capabilities... More than 40 years of experience handling liquid and sodium cyanide An extensive family of intermediates and derivatives Fast and reliable development and production of specialty intermediates esearch and development support Process development and optimization Complete analytical services Full scale-up support in the U.S. and Europe Flexible multi-purpose production facilities Large commercial capacity in two dedicated plants Schotten-Baumann acylation expertise Supported by The Dow Chemical Company s global resources The world of hydrogen cyanide chemistry offers many possibilities... Amino Amides: Glycinamide Cl, Cycloleucine amide Cl Acylated Amino Acids: Acyl Glutamates, Acyl Sarcosinates, -Lauroylethylenediamine-,, -triacetic acid (LED3A) Amino Acids: Glycine, Sarcosine, Amino Isobutyric Acid, Amino Cyclohexane Carboxylic Acid, Cycloleucine Amino Esters: Methyl Glycinate Cl, Ethyl Glycinate Cl, Methyl Sarcosinate Cl, Ethyl Sarcosinate Cl Amino itriles: Acetone Amino itrile, Cyclohexanone Amino itrile, (Dimethylamino) acetonitrile, Methyl Ethyl Ketone Amino itrile, Methyl Isobutyl Ketone Amino itrile Amino Polycarboxylic Acids: Ethylenediamine-,, -triacetic acid (ED3A), Iminodiacetic Acid Chiral Molecules: ()-Mandelic acid, ()-2- Chloromandelic acid, D-(4-ydroxyphenyl)glycine, D-(4-ydroxybutyl)glycine Cyanohydrins: Acetone Cyanohydrin, Methyl Ethyl Ketone Cyanohydrin, Mandelonitrile ydantoins: 5,5-Dimethylhydantoin, 5-Ethyl-5-methylhydantoin, 5-Phenylhydantoin, 5-(4-ydroxybutyl)hydantoin -ydroxy Acids: -ydroxyisobutyric Acid, Mandelic Acid -Keto Acids: Phenylpyruvic Acid, 3-Methyl-2- oxobutanoic Acid, 4-Methyl-2-oxopentanoic Acid itriles: 1,6-Dicyanohexane, Isophorone itrile Miscellaneous: Pantolactone, 5,5-Dimethyl-2, 4-oxazolidinedione, 2-ydroxyisobutyramide, Methyl Mandelate 3

4 ur Product Families Dow altermann Custom Processing s extensive familiarity with hydrogen cyanide chemistry and its many reaction products makes us a uniquely qualified resource for helping you achieve optimum production efficiency and economy. Following are brief descriptions of our hydrogen cyanide product families. -Amino Acids Acylated Amino Acids 1. / '' 2 ' C 2 2 glycine C 2 ' 2. a / C 2 sarcosine '' -Amino acids are prepared by reacting either sodium cyanide (Bersworth Chemistry) or hydrogen cyanide (Singer Chemistry) with an aldehyde or a ketone and an amine. Singer Chemistry provides the advantage of higher purity products due to isolation of the intermediate amino nitrile. -Amino acids and aminopoly-carboxylic acids (chelating agents) are commonly used as pharmaceutical, nutraceutical, and agricultural intermediates, as well as common components in cleaning, personal care, and photographic formulations. C 2 Me ' base C2 acyl sarosinates Cl acyl glutamates C 2 C2 -Amino acids are acylated using the Schotten- Baumann reaction, a core technology for Dow. Acylated amino acids are used in a variety of applications including personal care, cleaning, polymer, as well as pharmaceutical and agricultural intermediates. ' C 2 C 2 2 C C 2 2 C C 2 iminodiacetic acid C a 2 C a 2 C C 2 a LED3A 2 ethylenediamine triacetic acid trisodium salt acyl cycloleucine amide 4

5 -Amino Esters and Amides 2 CI '' ' CI solvent 2 3 -Amino esters and -amino amides can be prepared from the corresponding carboxylic acids, acid chlorides, or acid anhydrides. A more direct pathway is from the amino nitrile eliminating the additional steps leading to the carboxylic acid derivatives described above. -Amino esters and -amino amides are commonly used as pharmaceutical and agricultural intermediates. 3 C 2 '' ' ' - Cl 2 - Cl Amino itriles 2 ' '' 2 acetophenone amino nitrile acetone amino nitrile 2 ' '' Amino nitriles are readily prepared from the reaction of aldehydes or ketones with hydrogen cyanide and anhydrous ammonia in the presence of a base. Amino nitriles are precursors to -amino acids, -amino amides, and -amino esters. Amino nitriles are also commonly used as precursors to azo bis initiators via oxidative coupling. 2 3 C 2 Et cyclopentanone amino nitrile ethyl glycinate glycinamide hydrochloride 3 C 2 Me glycinonitrile dimethylaminoacetonitrile methyl phenylglycinate 3 2 cycloleucine amide C 2 Et ethyl sarcosinate 5

6 ()-pantolactone Chiral Molecules ' ()-oxynitrilase itrilase 2 C 2 L-6-hydroxynorleucine ' C 2 4 Chiral molecules are critical intermediates in a majority of the new pharmaceutical and agricultural products developed today. Three enzymes, oxynitrilase, hydantoinase, and nitrilase are useful in preparing chiral cyanohydrins, amino acids, and hydroxy acids. All of these specialties are useful intermediates leading to a variety of chiral molecules. Dow has used oxynitrilase enzymes commercially and is developing pathways leading to new chiral molecules using both of these enzymes. Cyanohydrins ' glycolonitrile base Cyanohydrins are common intermediates leading to a variety of molecules including amino nitriles, -hydroxy acids, amides, esters,, -unsaturated nitriles, acids, and esters. Cyanohydrins are readily prepared by reacting aldehydes and ketones with hydrogen cyanide in the presence of a base. The simplest cyanohydrin is glycolonitrile and it is frequently used to prepare aminopolycarboxylic acids (chelating agents). Acetone cyanohydrin, another common cyanohydrin, is a key intermediate in the preparation of methacrylic acid. Chiral cyanohydrins can be prepared using chemical resolving agents and with oxynitrilase enzymes leading to a variety of chiral entities. ' mandelonitrile acetone cyanohydrin 6

7 ydantoins ' 3 / C 2 ' itriles X base ydantoins are prepared using the well-known Bucherer-Bergs reaction, which involves the reaction of an aldehyde or a ketone with hydrogen cyanide, ammonia, and carbon dioxide. Dimethylhydantoin (DM) is a key intermediate in the preparation of brominated and chlorinated biocides. Substituted hydantoins are used as intermediates to many pharmaceuticals and can be hydrolyzed to form -substituted amino acids. ptically active unnatural amino acids can be prepared using D-hydantoinase enzymes. hydantoin Ph phenylhydantoin C base C itriles are prepared via nucleophilic substitutions of alky halides using an alkaline form of hydrogen cyanide. Michael Additions are common methods for the preparation of nitriles by the addition of hydrogen cyanide to activated double bonds in the presence of an alkaline catalyst. Substituted amines, prepared by the reduction of alkyl and aryl nitriles, are used in a variety of pharmaceutical, agricultural, and industrial applications. 1,6-dicyanohexane isophorone nitrile 5-(4-hydroxybutyl)hydantoin 5,5-dimethylhydantoin DMDM 7

8 To Learn More... ydrogen cyanide chemistry from Dow altermann Custom Processing offers a world of processing possibilities for a diverse range of chemical components and final products. We welcome your inquiries regarding our custom and toll synthesis capabilities and how we might put them to work for your process or application. Visit us on the web at r call In the United States and Canada: In Europe: Dedicated manufacturing facilities in Deer Park, Texas, and Seal Sands, UK TICE: o freedom from any patent owned by Seller or others is to be inferred. Because use conditions and applicable laws may differ from one location to another and may change with time, Customer is responsible for determining whether products and the information in this document are appropriate for Customer s use and for ensuring that Customer s workplace and disposal practices are in compliance with applicable laws and other governmental enactments. Seller assumes no obligation or liability for the information in this document. WAATIES AE GIVE; ALL IMPLIED WAATIES F MECATABILITY FITESS F A PATICULA PUPSE AE EXPESSLY EXCLUDED. * *Trademark of The Dow Chemical Company Form o AMS