Propene synthesis

Until the middle of last century, glycerol was mostly obtained as a co-product of soap fabrication. Afterwards, glycerol was also produced firom propene synthesis (route represented in Fig. 4.3) and more recently, when many countries started to produce biodiesel in large scales to partially substitute the traditional diesel of... 

Fig. 4.3 Routes of glycerol production, (i) Production of biodiesel and glycerol from transesterification reaction (ii) Industrial route for production of glycerol from propene synthesis...

The synthesis of 3-phenyl-]-(2-pyridyl)-2-propen-]-one (2.4c) via an aldol reaction of 2-acetylpyridine with benzaldehyde has been described in the literature ". O jmpound 2.4a-e have been prepared in high yields, using slightly modified versions of these literature procedures. 

Carbonylation of halides in the presence of primary and secondary amines at I atm affords amides[351j. The intramolecular carbonylation of an aryl bromide which has amino group affords a lactam and has been used for the synthesis of the isoquinoline alkaloid 498(352], The naturally occurring seven-membered lactam 499 (tomaymycin, neothramycin) is prepared by this method(353]. The a-methylene-d-lactam 500 is formed by the intramolecular carbonylation of 2-bromo-3-alkylamino-l-propene(354]. 

PROPENE The major use of propene is in the produc tion of polypropylene Two other propene derived organic chemicals acrylonitrile and propylene oxide are also starting materials for polymer synthesis Acrylonitrile is used to make acrylic fibers (see Table 6 5) and propylene oxide is one component in the preparation of polyurethane polymers Cumene itself has no direct uses but rather serves as the starting material in a process that yields two valuable indus trial chemicals acetone and phenol... 

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. 

Although not of industrial importance, many organometallic approaches have been developed (38). A one-pot synthesis of vitamin has been described and is based on the anionic [4 + 2] cycloaddition of three-substituted isoben2ofuranones to l-phytyl-l-(phenylsulfonyl)propene. Owing to the rather mild chemical conditions, the (H)-stereochemistry is retained (39). 

Schreiber found that the monoalkylation of the lithium enolate of cyclonona-none with propene oxide could be cleanly effected by addition of AlMe3 to give the y-hydroxy ketone 145, a key intermediate for the synthesis of recifeiolide [69a]. 

In 1950 the Fischer-Tropsch synthesis was banned in Germany by the allied forces. Sinarol, a high paraffinic kerosene fraction sold by Shell, was used as a substitute. This ban coincided with the rapid development of the European petrochemical industry, and in due time Fischer-Tropsch synthesis applied to the production of paraffins became uneconomic anyway. After the war there was a steady worldwide increase in the demand for surfactants. In order to continually meet the demand for synthetic detergents, the industry was compelled to find a substitute for /z-paraffin. This was achieved by the oligomerization of the propene part of raffinate gases with phosphoric acid catalyst at 200°C and about 20 bars pressure to produce tetrapropene. Tetrapropene was inexpensive, comprising a defined C cut and an olefinic double bond. Instead of the Lewis acid, aluminum chloride, hydrofluoric acid could now be used as a considerably milder, more economical, and easier-to-handle alkylation catalyst [4],... 

Alkenes can add to double bonds in a reaction different from those discussed in 15-19, which, however, is still formally the addition of RH to a double bond. This is called the ene reaction or the ene synthesis For the reaction to proceed without a catalyst, one of the components must be a reactive dienophile (see 15-58 for a definition of this word) such as maleic anhydride, but the other (which supplies the hydrogen) may be a simple alkene such as propene. Cyclopropene has also been used. ° The reaction is compatible with a variety of functional groups that can be appended to the ene and dienophile. N,N-Diallyl amides give an ene cyclization. 

Diazomalonic esters serve as intermediates for the synthesis of a wide variety of compounds including cyclopropanes, cyclo-propenes, cycloheptatrienes, sulfur ylides, lactones, and substituted malonates. ... 

Hydroformylation is an important industrial process carried out using rhodium phosphine or cobalt carbonyl catalysts. The major industrial process using the rhodium catalyst is hydroformylation of propene with synthesis gas (potentially obtainable from a renewable resource, see Chapter 6). The product, butyraldehyde, is formed as a mixture of n- and iso- isomers the n-isomer is the most desired product, being used for conversion to butanol via hydrogenation) and 2-ethylhexanol via aldol condensation and hydrogenation). Butanol is a valuable solvent in many surface coating formulations whilst 2-ethylhexanol is widely used in the production of phthalate plasticizers. 

As a new kind of carbon materials, carbon nanofilaments (tubes and fibers) have been studied in different fields [1]. But, until now far less work has been devoted to the catalytic application of carbon nanofilaments [2] and most researches in this field are focused on using them as catalyst supports. When most of the problems related to the synthesis of large amount of these nanostructures are solved or almost solved, a large field of research is expected to open to these materials [3]. In this paper, CNF is tested as a catalyst for oxidative dehydrogenation of propane (ODP), which is an attractive method to improve propene productivity [4]. The role of surface oxygen annplexes in catalyzing ODP is also addressed. 

Several other important commercial processes need to be mentioned. They are (not necessarily in the order of importance) the low pressure methanol process, using a copper-containing catalyst which was introduced in 1972 the production of acetic add from methanol over RhI catalysts, which has cornered the market the methanol-to-gasoline processes (MTG) over ZSM-5 zeolite, which opened a new route to gasoline from syngas and ammoxidation of propene over mixed-oxide catalysts. In 1962, catalytic steam reforming for the production of synthesis gas and/or hydrogen over nickel potassium alumina catalysts was commercialized. 

Hexamethylenediamine (HMDA), a monomer for the synthesis of polyamide-6,6, is produced by catalytic hydrogenation of adiponitrile. Three processes, each based on a different reactant, produce the latter coimnercially. The original Du Pont process, still used in a few plants, starts with adipic acid made from cyclohexane adipic acid then reacts with ammonia to yield the dinitrile. This process has been replaced in many plants by the catalytic hydrocyanation of butadiene. A third route to adiponitrile is the electrolytic dimerization of acrylonitrile, the latter produced by the ammoxidation of propene. 

The synthesis of aldehydes from alkenes known as hydroformylation using CO and hydrogen and a homogeneous catalyst is a very important industrial process [204]. Today, over seven million tons of oxoproducts are formed each year using this procedure, with the majority of butanal and butanol from propene. To further increase the efficiency of this process it can be combined with other transformations in a domino fashion. Eilbracht and coworkers [205] used a Mukaiyama aldol reaction as a second step, as shown for the substrate 6/2-63 which, after 3 days led to 6/2-65 in 91% yield via the primarily formed adduct 6/2-64 (Scheme 6/2.13). However, employing a reaction time of 20 h gave 6/2-64 as the main product. 

Nitroethylene, 1-nitro-l-propene and 2-nitro-l-propene, see Encyclopedia of Reagents for Organic Synthesis, ed. by L. Paquette, Wiley, New York, 1996. 

A simple synthesis of allethrolone, the alcohol component of the allethrine (commercially important insecticide), is shown in Scheme 4.11. The conjugated addition of 3-phenylthio-5-hexene-2-one to 1-nitro-l-propene followed by the Nef reaction and aldol condensation gives allethrolone in good yield.68... 

Propene is used as a starting material for the synthesis of acetone, cumene (isopropylbenzene), and polypropylene (PP). 

Sulfur dioxide has long been used in an industrial synthesis of isothiazole from propene, sulfur dioxide, and ammonia over a catalyst at 200°C.51... 

---