Side-products

CVD gaseous reactants (precursors) delivered to a heated substrate in a flow reactor undergo tliennal reaction to deposit solid films at atmospheric or reduced pressure, and volatile side products are pumped away. CVD is used for conductors, insulators and dielectrics, elemental semiconductors and compound semiconductors and is a workliorse in tire silicon microelectronics industry. 

Apart from using an environmentally friendly solvent, it is also important to clean up the chemical reactions themselves by reducing the number and amount of side-products formed. For this purpose catalysts are a versatile tool. Catalysts have been used for thousands of years in processes such as fermentation and their importance has grown ever since. In synthetic oiganic chemistry, catalysts have found wide applications. In the majority of these catalytic processes, organic solvents are used, but also here the use of water is becoming increasingly popular . 

Finally, it must be restated that the biggest plus of this method is that it produces 70-80% MD-P2P or P2P, and 20-30% isosafrole or propenylbenzene as a side product. So if the chemist were to turn around and process that isosafrole using, say, the formic acid method 1, then the potential P2P production from this method could climb to well over 90% ... 

When doing this method the scientists confirmed something that has long been theorized by those who study these sorts of things. That is, they determined that if one tries to convert all of the catechol at once like was done in the above method then it tends to form a dimer side product like that shown below [120]. 

Thus a second method was envisaged, the reaction of a nitrile, hydrogen selenide, and an a-halogenated ketone in the presence of a condensation catalyst, which can be POCl, or POCI3 with a Lewis acid such as PCI3 or anhydrous ZnCl. The use of fresh AICI3 leads to the formation of tarry side-products. 

Production, Processing, and Shipment. Hardboards and hardboard siding are fiber-base panel products having densities in the 500—1000-kg/m range. Two density classes are made medium density at 500—880 kg/m and high density, >880 kg/m . Hardboards are generally thin products, 2.5—9.5 mm in thickness, whereas the siding products are usually 11.1—12.7 mm in thickness. 

If the hydrogen could be reduced, the coproduction of hydrogen and valuable side products, eg, sulfur, sulfuric acid, and calcium sulfate, from H2S could become economically competitive. 

The reaction of dihalocarbenes with isoprene yields exclusively the 1,2- (or 3,4-) addition product, eg, dichlorocarbene CI2C and isoprene react to give l,l-dichloro-2-methyl-2-vinylcyclopropane (63). The evidence for the presence of any 1,4 or much 3,4 addition is inconclusive (64). The cycloaddition reaction of l,l-dichloro-2,2-difluoroethylene to isoprene yields 1,2- and 3,4-cycloaddition products in a ratio of 5.4 1 (65). The main product is l,l-dichloro-2,2-difluoro-3-isopropenylcyclobutane, and the side product is l,l-dichloro-2,2-difluoro-3-methyl-3-vinylcyclobutane. When the dichlorocarbene is generated from CHCl plus aqueous base with a tertiary amine as a phase-transfer catalyst, the addition has a high selectivity that increases (for a series of diolefins) with a decrease in activity (66) (see Catalysis, phase-TRANSFEr). For isoprene, both mono-(l,2-) and diadducts (1,2- and 3,4-) could be obtained in various ratios depending on which amine is used. 

Utilize the suciose-containing trisaccharide raffiaose [512-69-6] as a substrate for levan synthesis, releasing the disaccharide melihiose as a side-product. 

At pH 4—6, the cure is slower than it is at pH 8 and higher, and much slower than at pH 1—3. Reactions at pH 4—6 resemble those on the more alkaline side, but with a substantial increase in side-products. This is partly the result of the low rates of the main reactions and partly the result of stable intermediates at this pH range. 

The i j -configuration of the 6,7-double bond in pre-vitamin D is critical to its subsequent thermal rearrangement to the active vitamin. A photochemical isomerization of pre-vitamin D to yield the inactive trans-isoTnen occurs under conditions of synthesis, and is especially detrimental if there is a significant short wavelength component, eg, 254 nm, to the radiation continuum used to effect the synthesis. This side reaction reduces overall yield of the process and limits conversion yields to ca 60% (71). Photochemical reconversion of the inactive side product, tachysterol, to pre-vitamin D allows recovery of the product which would otherwise be lost, and improves economics of the overall process (70). 

Homogeneous rhodium-catalyzed hydroformylation (135,136) of propene to -butyraldehyde (qv) was commercialized in 1976. -Butyraldehyde is a key intermediate in the synthesis of 2-ethyIhexanol, an important plasticizer alcohol. Hydroformylation is carried out at <2 MPa (<290 psi) at 100°C. A large excess of triphenyl phosphine contributes to catalyst life and high selectivity for -butyraldehyde (>10 1) yielding few side products (137). Normally, product separation from the catalyst [Rh(P(C2H2)3)3(CO)H] [17185-29-4] is achieved by distillation. 

The characterizations of MDA and PMDA are similar to those normally used for aromatic amines. In the manufacture of PMDA, the MDA isomer distribution and the formation of side products is deterrnined primarily by gas chromatography (48,49). The amine content is deterrnined by acid titration... 

By-Products. Almost all commercial manufacture of pyridine compounds involves the concomitant manufacture of various side products. Liquid- and vapor-phase synthesis of pyridines from ammonia and aldehydes or ketones produces pyridine or an alkylated pyridine as a primary product, as well as isomeric aLkylpyridines and higher substituted aLkylpyridines, along with their isomers. Furthermore, self-condensation of aldehydes and ketones can produce substituted ben2enes. Condensation of ammonia with the aldehydes can produce certain alkyl or unsaturated nitrile side products. Lasdy, self-condensation of the aldehydes and ketones, perhaps with reduction, can lead to alkanes and alkenes. 

Nitrile Intermediates. Most quaternary ammonium compounds are produced from fatty nitriles (qv), which are ia turn made from a natural fat or oil-derived fatty acid and ammonia (qv) (Fig. 2) (see Fats AND FATTY oils) (225). The nitriles are then reduced to the amines. A variety of reduciag agents maybe used (226). Catalytic hydrogenation over a metal catalyst is the method most often used on a commercial scale (227). Formation of secondary and tertiary amine side-products can be hindered by the addition of acetic anhydride (228) or excess ammonia (229). In some cases secondary amines are the desired products. 

Distributors in industrial units typically have large numbers of injection points of quite diverse design characteristics, some of which are depicted in Eigure 16 for fluidized-bed appHcations. Flow variations through these parallel paths can lead to poor flow distributions within a reactor, thus reducing product yields and selectivity. In some circumstances, undesirable side products can foul portions of the distributor and further upset flow patterns. Where this is important, or where the possibiHties and consequences are insufficiently understood and independent means caimot be employed to assure adequate distribution, the pilot plant must be sized to accommodate such a distributor. Spacing should be comparable to those distributors that are anticipated to be... 

The NOBS system undergoes an additional reaction that forms a diacyl peroxide as a result of the nucleophilic attack of the peracid anion on the NOBS precursor as shown in equation 21. This undesirable side reaction can be minimized by the use of an excess molar quantity of hydrogen peroxide (91,96) or by the use of shorter dialkyl chain acid derivatives. However, the use of these acid derivatives also appears to result in less efficient bleaching. The dependence of the acid group on the side product formation is apparentiy the result of the proximity of the newly formed peracid to unreacted NOBS in the micellar environment (91). A variety of other peracid precursor stmctures can be found (97—118). 

Amino-6-chloro-4-methyl- and 3-amino-6-chloro-5-methyl-pyridazine and 3-amino-6-methylpyridazin-4(l//)-one are transformed with sodium nitrite in the presence of acid into the corresponding oxo compounds. If concentrated hydrochloric acid is used, in some instances the corresponding chloro derivatives are obtained as side products. On the other hand, 3-, 4-, 5- and 6-aminopyridazine 1-oxides and derivatives are transformed into stable diazonium salts, which can easily be converted into the corresponding halo derivatives. In this way 3-, 4-, 5- and 6-bromopyridazine 1-oxides, 5-chloropyridazine 1-oxide, 3,4,5-trichloropyridazine 1-oxide and 6-chloropyridazine 1-oxide can be obtained. 

Benzisoxazole or 3-methyl-2,l-benzisoxazole when treated with KNO3 in sulfuric acid produced the 5-nitro compound as the main product, with some of the 7-nitro as a side product (6.3MI41601, 65CC408). 

Benzisoxazoles were obtained from quinazolin-3-ols in an ArF displacement activated by Mn02 (equation 62) (74JHC885). The 1,2-benzisoxazole was produced as a minor side product in the reaction of (563) with hydroxylamine (73MI41600). 

The reaction of vinylogous amides, or ketoaldehydes, with hydroxylamine produced 4,5,6,7-tetrahydro-l,2-benzisoxazole. A side product is the 2,1-benzisoxazole (Scheme 173) (67AHC(8)277). The ring system can also be prepared by the reaction of cyclohexanone enamines with nitrile oxides (Scheme 173) (78S43, 74KGS901). Base treatment produced ring fission products and photolysis resulted in isomerization to benzoxazoles (76JOC13). 

Two extreme mechanisms can be envisaged (Scheme 12), concerted [2 + 2] cycloaddition or the more generally accepted formation of a dipolar intermediate (164) which closes to a /3-lactam or which can interact with a second molecule of ketene to give 2 1 adducts (165) and (166) which are sometimes found as side products. In some cases 2 1 adducts result from reaction of the imine with ketene dimer. 

Two disadvantages are associated with the use of S-acetyl or 5-benzoyl derivatives in peptide syntheses (a) base-catalyzed hydrolysis of 5-acetyl- and 5-benzoylcys-teine occurs with /S-elimination to give olefinic side products, CH2=C-(NHPG)CO—(b) the yields of peptides formed by coupling an unprotected amino group in an 5-acylcysteine are low because of prior S-N acyl migration. ... 

Thermodynamics. Along with stated yields goes heat requirements for the reactor. The thermodynamics for this operation should be checked, as the author once did for a proposed ethyl-benzene dehydrogenation process. Ethylbenzene and steam w-ere fed to the reactor, and unreacted ethyl-benzene and steam exited the reactor together with the sought product, styrene, and eight side products. 

In these cases the monomer is converted into polymer, and no side products are formed. This approach is used with the major thermoplastics materials (Figure 2.2) such as polyethylene (a polymer of ethylene), polystyrene (a polymer of styrene) and poly(methyl methacrylate) (a polymer of methyl methacrylate). 

The plant s product was hexachlorophene, a bactericide, with trichlorophenol produced ns an intermediate. During normal operation, a very small amount of TCDD (2,3,7,8 telrachlomdib zoparadioxin) is produced in the reactor as an undesirable side product. TCDD is perhaps the most ]in(enl toxin known to man. Studies have shown TCDD to be fatal in doses as small as lE-9 times die body weight, it insolubility in water makes decontamination very difficult. Nonlethal doses of TCDD result in chloracne, an acne-like disea.se that can persist for several years. 

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