Butadiene acid from

It has been known since the early 1950s that butadiene reacts with CO to form aldehydes and ketones that could be treated further to give adipic acid (131). Processes for producing adipic acid from butadiene and carbon monoxide [630-08-0] have been explored since around 1970 by a number of companies, especially ARCO, Asahi, BASF, British Petroleum, Du Pont, Monsanto, and Shell. BASF has developed a process sufficiendy advanced to consider commercialization (132). There are two main variations, one a carboalkoxylation and the other a hydrocarboxylation. These differ in whether an alcohol, such as methanol [67-56-1is used to produce intermediate pentenoates (133), or water is used for the production of intermediate pentenoic acids (134). The former is a two-step process which uses high pressure, >31 MPa (306 atm), and moderate temperatures (100—150°C) (132—135). Butadiene,... 

Ethanol s use as a chemical iatemiediate (Table 8) suffered considerably from its replacement ia the production of acetaldehyde, butyraldehyde, acetic acid, and ethyUiexanol. The switch from the ethanol route to those products has depressed demand for ethanol by more than 300 x 10 L (80 x 10 gal) siace 1970. This decrease reflects newer technologies for the manufacture of acetaldehyde and acetic acid, which is the largest use for acetaldehyde, by direct routes usiag ethylene, butane (173), and methanol. Oxo processes (qv) such as Union Carbide s Low Pressure Oxo process for the production of butanol and ethyUiexanol have totaUy replaced the processes based on acetaldehyde. For example, U.S. consumption of ethanol for acetaldehyde manufacture declined steadily from 50% ia 1962 to 37% ia 1964 and none ia 1990. Butadiene was made from ethanol on a large scale duriag World War II, but this route is no longer competitive with butadiene derived from petroleum operations. 

Other nylons are made by varying the molecular length of the diamines and the dibasic acids Nylon-fi. in u.ses sebacic acid (10 carbon atoms), nylon-11 uses an acid from castor oil, and nylon-12 uses butadiene. These variations decrease moisture absorption. Other variations use amines with a ring structure, e.g., the aromatic nylons to give polymers with softening points above 577 F,... 

The presence of the catalyst can also favor multiple Diels-Alder reactions of cycloalkenones. Two typical examples are reported in Schemes 3.6 and 3.7. When (E)-l-methoxy-1,3-butadiene (14) interacted with 2-cyclohexenone in the presence of Yb(fod)3 catalyst, a multiple Diels-Alder reaction occurred [21] and afforded a 1 1.5 mixture of the two tricyclic ketones 15 and 16 (Scheme 3.6). The sequence of events leading to the products includes the elimination of methanol from the primary cycloadduct to afford a bicyclic dienone that underwent a second cycloaddition. Similarly, 4-acetoxy-2-cyclopenten-l-one (17) (Scheme 3.7) has been shown to behave as a conjunctive reagent for a one-pot multiple Diels-Alder reaction with a variety of dienes under AICI3 catalysis, providing a mild and convenient methodology to synthesize hydrofluorenones [22]. The role of the Lewis acid is crucial to facilitate the elimination of acetic acid from the cycloadducts. The results of the reaction of 17 with diene... 

On the other hand, several examples of chiral sulfonamides derived from ehiral a-amino acids have been successfully employed as ligands for enantio-seleetive Diels-Alder reactions. Thus, Yamamoto and Takasu have easily prepared new chiral Lewis acids from borane and sulfonamides of various ehiral a-amino acids, which were further studied for their abilities to promote the enantioselective Diels-Alder reaction between methacrolein and 2,3-dime-thyl-1,3-butadiene. Since 2,4,6-triisopropylbenzenesulfonamide of a-amino-butyric acid gave the highest enantioseleetivity, this eatalyst was applied to the... 

Brandt [200] has extracted tri(nonylphenyl) phosphite (TNPP) from a styrene-butadiene polymer using iso-octane. Brown [211] has reported US extraction of acrylic acid monomer from polyacrylates. Ultrasonication was also shown to be a fast and efficient extraction method for organophosphate ester flame retardants and plasticisers [212]. Greenpeace [213] has recently reported the concentration of phthalate esters in 72 toys (mostly made in China) using shaking and sonication extraction methods. Extraction and analytical procedures were carefully quality controlled. QC procedures and acceptance criteria were based on USEPA method 606 for the analysis of phthalates in water samples [214]. Extraction efficiency was tested by spiking blank matrix and by standard addition to phthalate-containing samples. For removal of fatty acids from the surface of EVA pellets a lmin ultrasonic bath treatment in isopropanol is sufficient [215]. It has been noticed that the experimental ultrasonic extraction conditions are often ill defined and do not allow independent verification. 

Compared with the anodic oxidation of a 1,3-diene, the cathodic reduction of a 1,3-diene may be less interesting since the resulting simple transformation to monoolefin and alkane is more conveniently achieved by a chemical method than by the electrochemical method. So far, only few reactions which are synthetically interesting have been studied15. The typical pattern of the reaction is the formation of an anion radical from 1,3-diene followed by its reaction with two molecules of electrophile as exemplified by the formation of the dicarboxylic acid from butadiene (equation 22)16. 

The reaction of 2,3-dimethyl-l,3-butadiene with an equimolar amount of chlorine in carbon tetrachloride at — 20 °C has instead been reported593 to give mainly trans-1,4-dichloro-2,3-dimethyl-2-butene and 2-chloromethyl-3-methyl-l,3-butadiene, arising from the loss of one of the acidic hydrogen atoms in the ionic intermediate (equation 28). 

Adipic acid is prepared commercially by oxidative processes using either benzene or phenol as the raw material base. Since both benzene and phenol prices track with the price of crude oil, future adipic acid price will increase as the oil reserve decreases(j ). Thus, there is a need for a new process to produce adipic acid from cheap, and readily available, raw materials such as butadiene, synthesis gas, and methanol. 

In basic chemicals, nitrile hydratase and nitrilases have been most successful. Acrylamide from acrylonitrile is now a 30 000 tpy process. In a product tree starting from the addition of HCN to butadiene, nicotinamide (from 3-cyanopyridine, for animal feed), 5-cyanovaleramide (from adiponitrile, for herbicide precursor), and 4-cyanopentanoic acid (from 2-methylglutaronitrile, for l,5-dimethyl-2-piperidone solvent) have been developed. Both the enantioselective addition of HCN to aldehydes with oxynitrilase and the dihydroxylation of substituted benzenes with toluene (or naphthalene) dioxygenase, which are far superior to chemical routes, open up pathways to amino and hydroxy acids, amino alcohols, and diamines in the first case and alkaloids, prostaglandins, and carbohydrate derivatives in the second case. 

Hoberg H, Gross S, Milchereit A (1987) Nickel(0)-catalyzed production of a functionalized cyclopentanecarboxylic acid from 1,3-butadiene and C02. Angew Chem Int Ed 26 571-572... 

In the BASF process the 1,2-diacetate is the substrate for the hydroformylation step. It can be prepared either directly via oxidative acetoxylation of butadiene using a selenium catalyst or via PtCl4-catalyzed isomerization of the 1,4-diacetate (see above). The latter reaction affords the 1,2-diacetate in 95% yield. The hydroformylation step is carried out with a rhodium catalyst without phosphine ligands since the branched aldehyde is the desired product (phosphine ligands promote the formation of linear aldehydes). Relatively high pressures and temperatures are used and the desired branched aldehyde predominates. The product mixture is then treated with sodium acetate in acetic acid to effect selective elimination of acetic acid from the branched aldehyde, giving the desired C5 aldehyde. 

A most important application of butadiene carbonylations is BASF s development of a three-stage process for the synthesis of adipic acid from the butadiene-containing C4 cut [1] (eqs. (4) and (5)). Cobalt is the catalyst metal of choice for this process. The reaction takes place in two steps the first stage, which involves a lower temperature (100-140 °C), uses a fairly high concentration of HCo(CO)4 and pyridine as catalyst system to ensure rapid carbonylation of butadiene to give methyl pent-3-enoate in 90 % selectivity, thus avoiding typical side reactions such as dimerization and oligomerization. 

Use Solvent in hydrocarbon extraction processes, especially for butadiene specialty solvent intermediate catalyst separation of fatty acids from vegetable oils manufacturing of synthetic pharmaceuticals. 

ABN rubber (acrylonitrile/butadiene/methacrylic acid, from Ciba Geigy) ... 

Acetonitril Acetonitrile AI3-00327 CCRIS 1628 Cyanomethane Cyanure de methyl EINECS 200-835-2 Ethyl nitrile HSDB 42 Methane, cyano- Methane-carbonitrile Methyl cyanide Methylkyanid NCI-C60822 NSC 7593 RCRA waste number U003 UN1648 USAF EK-488. Solvent for hydrocarbon extraction processes, especially for butadiene intemnediate catalyst for separation of fatty acids from vegetable oils manufacture of synthetic pharmaceuticals. Liquid mp = -43.8° bp = 81.6° d20 =... 

I.r. emission has been seen from the vibrationally excited CO2 product of MPD of vinylacetic and pyruvic acids, from hydrogen halides formed by chemical reaction of CI2 with H atoms produced in the MPD of various hydrocarbons, and of HBr with F and Cl atoms formed in the MPD of CFjCl. Infrared fluorescence from CjFjCl following MPA shows emission from both discrete levels and the quasicontinuum, with efficient intramolecular vibrational redistribution out of the pumped mode evident after absorption of only 2—3 photons. Emission in the i.r. has been seen following MPA in N2p4, and has been used to study the interconversion of perfluorocyclobutene to perfluoro-butadiene isomers following MPA. Further isomerization reactions induced by CO2 lasers have been reported. 

An important variation in butadiene polymerization technology is the reductive dimerization of butadiene, using stoichiometric, instead of catalytic, quantities of sodium. This process has been developed by National Distillers into a commercial synthesis of a mixture of 10-carbon dicarboxylic acids, and a 10,000,000-pound-per-year plant is under construction to exploit this reaction (7). Esso has recently developed a similar process for the synthesis of dimeric dicarboxylic acids from the reaction between sodium and cyclopentadiene, but there has been no indication yet that it intends to commercialize this reaction (8). 

Polymer characterization is an important use of NIR spectrometry. Polymers can be made either from a single monomer, as is polyethylene, or from mixtures of monomers, as are styrene-butadiene rubber from styrene and butadiene and nylon 6-6, made from hexamethylenediamine and adipic acid. An important parameter of such copolymers is the relative amount of each present. This can be determined by NIR for polymers with the appropriate functional groups. Styrene content in a styrene-butadiene copolymer can be measured using the aromatic and aliphatic C—H bands. Nylon can be characterized by the NH band from the amine monomer and the C=0 band from the carboxylic acid monomer. Nitrogen-containing polymers such as nylons, polyurethanes, and urea formaldehyde resins can be measured by using the NH bands. Block copolymers, which are typically made of a soft block of polyester and a hard block containing aromatics, for example, polystyrene, have been analyzed by NIR. These analyses have utilized the... 

Thermal cycloaddition reactions of chiral 1-acyloxy-1,3-butadienes derived from chiral carboxylic acids >vith electron-deficient alkenes, e.g. A -ethylmaleimide or quinones, were found to be highly endo selective. Moderate to high diastereoselectivities were obtained (>96 4). 

Batch Di (3-pentyl) Malate Process Acetaldehyde from Acetic Acid Ethylene by Oxidative Dehydrogenation of Ethane Butadiene to n-Butyraldehyde and n-Butanol Methacrylic Acid to Methylmethacrylate Coproduction of Ethylene and Acetic Acid from Ethane Methylmethacrylate from Propyne Mixed-C4 Byproduct Upgrade Hydrogen Peroxide Manufacture Di-tem fljy-butyl-peroxide Manufacture Vinyl Acetate Process PM Acetate Manufacture Propoxylated Ethylenediamine Petroleum Products Fuel Additives for Cleaner Emissions Gas Manufacture... 

Nonracemic l-methoxy-3-sulfinyl-l,3-butadienes derived from 10-mercapto-isobomeol have been prepared by the cycloaddition of (15)-isobornyl-10-sulfenic acid to (Z)- and ( )-l-methoxybut-l-en-3-yne. High levels of asymmetric induction were observed for the cycloaddition in some cases [40]. 

Danishefsky and coworkers have used the racemic P-phenylsulfinyl-a,P-unsaturated ketone (160) as an a,P-ethynyl carbonyl synthetic equivalent and found that the phenylsulflnyl group did not compete with the carbonyl group in determining the regioselectivity of cycloaddition with the l-methoxy-3-trimethylsilyloxy-1,3-butadiene (161), now known as Danishefsky s diene [140] (Scheme 5.54). Loss of methanol and phenyl sulfenic acid from the initial cycloadduct (162) gave the aromatic product (163). 

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