Dimethyl application

H-Chromene, 6,7-dimethoxy-2,2-dimethyl-application, 3, 881 2H-Chromene, 2,2-dimethyl-addition reactions, 3, 670 fluorinated... 

Pyrimido[4,5-c]pyridazine-5,7-dione, 1,5,6,7-tetrahydro-1,6-dimethyl-applications, 3, 367... 

Chromene, 7-methoxy-2,3-dimethyl-application, 3, 881 2//-Chromene, 2-methyl-mass spectra, 3, 603 2//-Chromene, 2-methyl-3-nitro-hydrogenation, 3, 673... 

J. Rebek, Jr., (1987) first developed a new synthesis of Kemp s acid and then extensively explored its application in model studies. The synthesis involves the straightforward hydrogenation (A. Steitz, 1968), esterification and methylation of inexpensive 1,3,5-benzenetricar-boxylic acid (trimesic acid 30/100 g). The methylation of the trimethyl ester with dimethyl sulfate, mediated by lithium diisopropylamide (V. J. Shiner, 1981), produced mainly the desired aff-cis-1,3,5-trimethyl isomer, which was saponified to give Kemp s acid. 

As an application of maleate formation, the carbonylation of silylated 3-butyn-l-ol affords the 7-butyrolactone 539[482], Oxidative carbonylation is possible via mercuration of alkynes and subsequent Lransmetallation with Pd(II) under a CO atmosphere. For example, chloromercuration of propargyl alcohol and treatment with PdCF (1 equiv.) under 1 atm of CO in THF produced the /3-chlorobutenolide 540 in 96% yield[483]. Dimethyl phenylinale-ate is obtained by the reaction of phenylacetylene, CO, PdCU, and HgCl2 in MeOH[484,485]. 

As illustrated in Scheme 8.1, both 2-vinylpyrroles and 3-vinylpyiroles are potential precursors of 4,5,6,7-tetrahydroindolcs via Diels-Alder cyclizations. Vinylpyrroles are relatively reactive dienes. However, they are also rather sensitive compounds and this has tended to restrict their synthetic application. While l-methyl-2-vinylpyrrole gives a good yield of an indole with dimethyl acetylenedicarboxylate, ot-substitiients on the vinyl group result in direct electrophilic attack at C5 of the pyrrole ring. This has been attributed to the stenc restriction on access to the necessary cisoid conformation of the 2-vinyl substituent[l]. 

Sandstrom et al. (65) evaluated the Kj value for 4,5-dimethyl-A-4-thiazoline-2-thione (46) in water (Scheme 19) K-j= 10. A-4-Thiazoline-2-thiones are less basic in the first excited state (61) than in the ground state, so application of Forster s cycle suggests that the thione form is even more favored in the first excited state. Huckel molecular orbital (HMO) calculations suggest that electronic effects due to substitution in... 

These methods were not applicable to all acids, and various alternative routes were investigated. The conversion of an acid to its methri ester by diazomethane is a method of choice when other methods are unsatisfactory (6, 30, 61, 65). With appropriate alcohols thiazoleanhydrkies give the esters or diesters in good yield (64), dimethyl 2-phoiyl-4,5-thiazoledicarboxylate (13) has been prepared in this way (Scheme 8) (17). 

Ester interchange reactions are valuable, since, say, methyl esters of di-carboxylic acids are often more soluble and easier to purify than the diacid itself. The methanol by-product is easily removed by evaporation. Poly (ethylene terephthalate) is an example of a polymer prepared by double application of reaction 4 in Table 5.3. The first stage of the reaction is conducted at temperatures below 200°C and involves the interchange of dimethyl terephthalate with ethylene glycol... 

Standard polyester fibers contain no reactive dye sites. PET fibers are typically dyed by diffusiag dispersed dyestuffs iato the amorphous regions ia the fibers. Copolyesters from a variety of copolymeri2able glycol or diacid comonomers open the fiber stmcture to achieve deep dyeabiHty (7,28—30). This approach is useful when the attendant effects on the copolyester thermal or physical properties are not of concern (31,32). The addition of anionic sites to polyester usiag sodium dimethyl 5-sulfoisophthalate [3965-55-7] has been practiced to make fibers receptive to cationic dyes (33). Yams and fabrics made from mixtures of disperse and cationicaHy dyeable PET show a visual range from subde heather tones to striking contrasts (see Dyes, application and evaluation). 

Uses. The chemical inertness, thermal stability, low toxicity, and nonflammability of PFCs coupled with their unusual physical properties suggest many useflil applications. However, the high cost of raw materials and manufacture has limited commercial production to a few, small-volume products. Carbon tetrafluoride and hexafluoroethane are used for plasma, ion-beam, or sputter etching of semiconductor devices (17) (see loN implantation). Hexafluoroethane and octafluoropropane have some applications as dielectric gases, and perfluorocyclobutane is used in minor amounts as a dielectric fluid. Perfluoro-1,3-dimethyl cyclohexane is used as an inert, immersion coolant for electronic equipment, and perfluoro-2-methyldecatin is used for... 

An important extension of these reactions is the Mannich reaction, in which aminomethyl-ation is achieved by the combination of formaldehyde, a secondary amine and acetic acid (Scheme 24). The intermediate immonium ion generated from formaldehyde, dimethyl-amine and acetic acid is not sufficiently reactive to aminomethylate furan, but it will form substitution products with alkylfurans. The Mannich reaction appears to be still more limited in its application to thiophene chemistry, although 2-aminomethylthiophene has been prepared by reaction of thiophene with formaldehyde and ammonium chloride. The use of A,iV-dimethyf (methylene) ammonium chloride (Me2N=CH2 CF) has been recommended for the iV,iV-dimethylaminomethylation of thiophenes (83S73). 

Actinocin — see Phenoxazine-l,9-dicarboxylic acid, 2-amino-4,6-dimethyl-3-oxo-Actinoleutin applications, 3, 195 Actinomycins... 

Benzo[b]furan, 2,3-dihydro-2-phenyl-synthesis, 4, 697 Benzo[b]furan, 2,3-dihydroxy-tautomerism, 4, 37 Benzo[6]furan, 4,6-dimethoxy-acylation, 4, 606 Benzo[6]furan, 2,3-dimethyl-acetylation, 4, 606 bromination, 4, 605 photooxygenation, 4, 642 Benzo[b]furan, 5,6-dimethyl-2,3-diphenyl-applications, 4, 709 Benzo[b]furan, 1,3-diphenyl-vertical ionization potential, 4, 587 Benzo[b]furan, 2-ethoxy-5-hydroxy-synthesis, 4, 127... 

NMR, 4, 575 Erythritol, 1,4-anhydro-structure, 4, 546 Erythromycin antibacterial veterinary use, 1, 206 as pharmaceutical, 1, 153 synthesis, 1, 480 Erythropterin biosynthesis, 3, 321 occurence, 3, 323 structure, 3, 276 synthesis, 3, 289 Erythropterin, 3,5-dimethyl-methyl ester synthesis, 3, 303 Erythrosine application, 3, 879 Esculetin... 

Paal-Knorr synthesis, 4, 118, 329 Pariser-Parr-Pople approach, 4, 157 PE spectroscopy, 4, 24, 188-189 photoaddition reactions with aliphatic aldehydes and ketones, 4, 232 photochemical reactions, 4, 67, 201-205 with aliphatic carbonyl compounds, 4, 268 with dimethyl acetylenedicarboxylate, 4, 268 Piloty synthesis, 4, 345 Piloty-Robinson synthesis, 4, 110-111 polymers, 273-274, 295, 301, 302 applications, 4, 376 polymethylation, 4, 224 N-protected, 4, 238 palladation, 4, 83 protonation, 4, 46, 47, 206 pyridazine synthesis from, 3, 52 pyridine complexes NMR, 4, 165... 

Pyrrolo[3,2-6]pyrrole, N,N -dimethyl-UV spectra, 4, 1044 Pyrrolo[3,2-6]pyrrole, octahydro-synthesis, 4, 1081 Pyrrolopyrroles H NMR, 4, 1041 occurrence, 4, 1042 reactivity, 4, 1049 synthesis, 4, 1068 Pyrrolo[2,3-6]pyrroles ionization potentials, 4, 1046 synthesis, 4, 293, 1070 Pyrrolo[3,2-6]pyrroles synthesis, 6, 1009 Pyrrolo[3,2-6]pyrroles, dihydrosynthesis, 4, 1081 Pyrrolo[3,4-c]pyrroles applications, 4, 1083 Pyrroloquinolines... 

Westphal synthesis, 2, 566 Woodward synthesis, 2, 551, 552 Quinolizinium salts, l-acetylamino-2,3-dimethyl-oxidation, 2, 540 Quinolizinium salts, 1-amino-synthesis, 2, 541 Quinolizinium salts, 2-amino-applications, 2, 569 diazotization, 2, 542 N-substituted... 

Although ethereal solutions of methyl lithium may be prepared by the reaction of lithium wire with either methyl iodide or methyl bromide in ether solution, the molar equivalent of lithium iodide or lithium bromide formed in these reactions remains in solution and forms, in part, a complex with the methyllithium. Certain of the ethereal solutions of methyl 1ithium currently marketed by several suppliers including Alfa Products, Morton/Thiokol, Inc., Aldrich Chemical Company, and Lithium Corporation of America, Inc., have been prepared from methyl bromide and contain a full molar equivalent of lithium bromide. In several applications such as the use of methyllithium to prepare lithium dimethyl cuprate or the use of methyllithium in 1,2-dimethyoxyethane to prepare lithium enolates from enol acetates or triraethyl silyl enol ethers, the presence of this lithium salt interferes with the titration and use of methyllithium. There is also evidence which indicates that the stereochemistry observed during addition of methyllithium to carbonyl compounds may be influenced significantly by the presence of a lithium salt in the reaction solution. For these reasons it is often desirable to have ethereal solutions... 

LPG is considered to be non-toxic witli no chronic effects, but the vapour is slightly anaesthetic. In sufficiently high concentrations, resulting in oxygen deficiency, it will result in physical asphyxiation. The gases are colourless and odourless but an odorant or stenching agent (e.g. methyl mercaptan or dimethyl sulphide) is normally added to facilitate detection by smell down to approximately 0.4% by volume in air, i.e. one-fifth of the lower flammable limit. The odorant is not added for specific applications, e.g. cosmetic aerosol propellant. 

With the discovery of the crowns and related species, it was inevitable that a search would begin for simpler and simpler relatives which might be useful in similar applications. Perhaps these compounds would be easier and more economical to prepare and ultimately, of course, better in one respect or another than the molecules which inspired the research. In particular, the collateral developments of crown ether chemistry and phase transfer catalysis fostered an interest in utilizing the readily available polyethylene glycol mono- or dimethyl ethers as catalysts for such reactions. Although there is considerable literature in this area, much of it relates to the use of simple polyethylene glycols in phase transfer processes. Since our main concern in this monograph is with novel structures, we will discuss these simple examples further only briefly, below. 

Proof of formula (VI) for dehydrolaudanosoline salts was provided by a study of its exhaustive methylation, the products at the first and second stages of the application of this process being 5 6-dimethoxy-2-(3 4 -dimethoxy-6 -vinylphenyl)-l-methyldihydroindole (VIII) and 6-dimethyl-amino-3 4 3 4 -tetramethoxy-6 -vinylstilbene (IX) respectively. 

Isotope labeling by derivative formation with deuterated reagents is useful for the preparation of analogs such as dg-acetonides, da-acetates, da-methyl ethers, dg-methyl esters, etc. The required reagents are either commercially available or can be easily prepared. (The preparation of da-methyl iodide is described in section IX-F. Various procedures are reported in the literature for the preparation of dg-acetone, da-diazometh-ane57.i63.i73 and da-acetyl chloride. ) These reactions can be carried out under the usual conditions and they need no further discussion. A convenient procedure has been reported for the da-methylation of sterically hindered or hydrogen bonded phenolic hydroxyl functions by using da-methyl iodide and sodium hydroxide in dimethyl sulfoxide solution. This procedure should be equally applicable to the preparation of estradiol da-methyl ether derivatives. 

In recent years the use of dimethyl sulfoxide (DMSO) as an oxidizing agent has found increasing application. This growing interest is undoubtedly due to the development of new methods which can be carried out under mild conditions, involve simple work-ups and give high yields of products. 

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