The README File

John H.MacMillan's Chemistry Preprint Articles Research and review articles on: Liquid crystals, organometallic compounds, silanes, silicones, platinum catalysts, organophosphines, homogeneous, heterogeneous catalysts, insulating glass sealants, Grignard reagents... Complete list of papers and patents of Dr. MacMillan can be found at: http://docs.google.com/Doc?docid=0AR2ideyPd9SLZGd3amM5ZmRfMTg3em05Z3Y5Zms&hl=en

File List for MacMillan Directory

• Vanadiun-Line-Broadening.pdf [3003kB] : T.R.P. Gibb Jr. and John H. MacMillan, Vanadium hydride x-ray line broadening
  The broadening of the x-ray diffraction lines of non stoichiometric vanadium hydrides of composition VH0.15 to VH0.80 were measured and compared to pure vanadium powder. The 110,200,211,220,310 and 321 diffraction planes line broadening were measured at all stoichiometries. In every case the 211 plane showed the greatest percentage broadening, followed by the 200 plane. The broadening order was 211>200>110=310>321.
  The results were interpreted to possibly indicate preferential distortion of the 211 plane due to its smallest unit cell area and greatest percentage lattice deformation on hydrogen occupancy of octahedral sites.
• bioconext.pdf [42kB] : A method for derivatizing surfaces with aldehyde groups by employing a new alkoxy aldehydic silane. Coyne, Ann. N., Benner, Lauren., MacMillan, John H., Telepchak, Michael T.
  A new line of trialkoxy aldehydic silanes, manufactured by United Chemical Technologies, Inc. under the trademark BIO-CONEXT, allows the one-step addition of an activated surface directly to a matrix, thus circumventing the steps and reagents required by other methods. In addition, the covalent linkage formed by this method has only one Schiff base, yielding a much more stable product. Furthermore, this method can be used with any matrix that has either naturally occurring or synthetically incorporated hydroxyl groups that can be synthetically modified with trialkoxy aldehyldic silanes. Included are some of the most popular and useful matrix materials, such as glass, agarose, silica, glass-coated ELISA plates, metals such as nickel and paramagnetic iron, and some commercially available resins1. In addition, incorporation of trialkoxy aldehydic silanes with different chain lengths can be used to prevent crowding of large bio-molecules and to allow access to active sites. In this report, we describe and evaluate the BIO-CONEXT method for covalent attachment of bio-molecules.
• Nitrones-2.pdf [3076kB] : Synthesis and Photochemistry of Chiral Liquid Crystalline Nitrones
  
• Grignard-addition-to-propargylic-allylic-alcohols.pdf [1467kB] : Addition of Grignard Reagents to Allylic and Propargylic Alcohols
  
• adhesion.pdf [408kB] : Using Silanes as Adhesion Promoters
  
• chemiker.pdf [1307kB] : Recent Examples of Selectivity in Catalysis
  
• formulating.pdf [2867kB] : Formulating Silicone Adhesives, Rubbers and Gels
  
• platinum.pdf [1587kB] : Homogeneous Platinum Catalysts
  
• acetylenes.pdf [944kB] : Vapor Phase Thermolysis of 1,5-Hexadiynes, Effect of Hydroxyl Substitution
  
• tmsa-benzoquinone-4.pdf [819kB] : Further Studies of the Interaction of Carbonyl Compounds with Organometallic Azides, the Novel Reaction of Benzoquinone with Trimethylsilylazide
  
• diphenylacetylene2.pdf [401kB] : An Improved Method for the Preparation of Bis-DiphenylPhosphino Acetylene and unsymmetrical Aryl Substituted Diphenylphosphino Acetylenes
  
• polyformals-2.pdf [3415kB] : Hexamethylene Glycol Polyformal Copolymers for Insulating Glass and Building Sealants
  
• ArylMaleic-Anhydrides.pdf [2185kB] : A Facile General Synthesis of Arylmaleic Anhydrides:
  By a sequence involving Knoevenagel condensation, Michael addition of cyanide, hydrolysis, and selenium dioxide oxidation, a series of seven aryl maleic anhydrides were prepared in excellent overall yields. The regiospecificity of reaction of these anhydrides with various nucleophilic species, e.g. Me3SiN3, NH3, and PhNH2 was investigated. Except for a few cases, the nucleophile attacks the more hindered carbonyl, in a reaction controlled by electronic rather than steric factors. These anhydrides are of particular utility in the synthesis of 4-and 5-Aryl Substituted 1,3(3H) Oxazine-2,6-Diones (Oxauracils).
  
• Oxauracils-Hydrolysis.pdf [4903kB] : Hydrolysis reactions of the 4-and 5-Alkyl or Aryl Substituted 1,3(3H) Oxazine-2,6-Diones (Oxauracil) Ring System
  Acid or base hydrolysis of 4-Aryl or alkyl Substituted 1,3(3H) Oxazine-2,6-Diones (Oxauracils)1,2 yield alkyl or aryl methyl ketones, 6, and ammonia. An intermediate beta keto acid, 5, could be isolated under mild conditions. N-alkylated oxauracils give the same methyl ketones and alkylamines. The N-alkylated oxauracils hydrolyze faster than the non alkylated oxauracils in competion experiments, probably due to electronic factors. 5-aryl oxauracils hydrolyze slower than the 4-isomers in direct competition experiments, probably due to steric factors at the C-6 carbonyl carbon. A mechanistic scheme is presented involving nucleophilic attack at the C-6 carbonyl, decarboxylation of the resulting amino acid 2 yielding enamine 3, which tautomerizes to imine 4. Hydrolysis of 4 and further decarboxylation of beta keto acid 5 give methyl ketones 6 in nearly quantitative yield. The in vitro toxicity of these products is low, thus is of little concern in genetic studies involving substitution ofoxauracils for uracils in RNA or other nucleotides.
  
• surface.pdf [38kB] : Silane Surface Modifying Reagents
  Industrial silane suppliers offer a wide range of polar and non-polar silanes which may be used to modify the surface of substrates such as glass, silica, alumina, silicon and transition metals. The surface may be treated to decrease wettability or increase adhesion of the polymer to glass, silicon or metals. Such treatment may also allow differential polar or hydrophobic interactions. The hydrophobic class represents alkyl functional alkoxy or chlorosilanes from C2-C22 chain length. They find use in decreasing the wettability of treated surfaces, as releasing agents and for increasing the hydrophobic interactions of treated sorbents with diluents in a mobile phase.
  
• MacMillan_PhD_Thesis.pdf [13016kB] : Triple Bond Participation in the Oxy-Cope Rearrangement (Ph.D. Thesis)