BASF route

The BASF route started from hydroquinone, which was converted to 2,5-dihydroterephthalic acid by a Kolbe-Schmitt reaction. One mole of this acid was treated with two moles of an arylamine, both components being in the form of a suspension in aqueous methanol. This was added to a small amount of a solution of vanadium(III) chloride and sodium chlorate. Gentle heating gave a 95% yield of 2,5-bis(arylamino)benzo-l,4-quinone-3,6-dicarboxylic acid. Ring closure to the trans-quinacridonequinone took place in the presence of concentrated sulphuric acid at 60-80 °C. This was then reduced to the required crude pigment by zinc or aluminium powder in caustic soda under pressure,in an aluminium chloride/urea melt or by the use of a sulphuric acid/polyphosphoric acid mixture. 

In the new BASF route, the cheap starting materials isobutene and formaldehyde are made to react to form isoprenol (3-methyl-but-3-en-l-ol). A part of this is isomerized and the other part is oxidised to the corresponding aldehyde (Scheme 27). 

On the other hand, new processes are being researched, such as i) the named Alpha process via ethylene carbonylation to methyl propionate, very similar to the aforementioned BASF route ii) the one-step method of propyne catal3dic carbonylation and iii) direct oxidation of isobutane to methacrolein or methacrylic acid. The use of isobutyraldehyde and isobutyric acid as feedstocks has also been explored. Among all these methods, the one employing the alkane in a one-step reaction to form methacrylic acid is the most simple and interesting process from both... 

In the 1980s cost and availabiUty of acetylene have made it an unattractive raw material for acrylate manufacture as compared to propylene, which has been readily available at attractive cost (see Acetylene-DERIVED chemicals). As a consequence, essentially all commercial units based on acetylene, with the exception of BASF s plant at Ludwigshafen, have been shut down. AH new capacity recendy brought on stream or announced for constmction uses the propylene route. Rohm and Haas Co. has developed an alternative method based on aLkoxycarbonylation of ethylene, but has not commercialized it because of the more favorable economics of the propylene route. 

Reppe s work also resulted in the high pressure route which was estabUshed by BASF at Ludwigshafen in 1956. In this process, acetylene, carbon monoxide, water, and a nickel catalyst react at about 200°C and 13.9 MPa (2016 psi) to give acryUc acid. Safety problems caused by handling of acetylene are alleviated by the use of tetrahydrofuran as an inert solvent. In this process, the catalyst is a mixture of nickel bromide with a cupric bromide promotor. The hquid reactor effluent is degassed and extracted. The acryUc acid is obtained by distillation of the extract and subsequendy esterified to the desked acryhc ester. The BASF process gives acryhc acid, whereas the Rohm and Haas process provides the esters dkecdy. 

Future Methanol Processes. The process route for methanol synthesis has remained basically unchanged since its inception by BASF in 1923. The principal developments have been in catalyst formulation to increase productivity and selectivity, and in process plant integration to improve output and energy efficiency while decreasing capital cost. 

The current paradigm for B syntheses came from the first report in 1957 of a synthesis of pyridines by cycloaddition reactions of oxazoles (36) (Fig. 5). This was adapted for production of pyridoxine shordy thereafter. Intensive research by Ajinomoto, BASF, Daiichi, Merck, Roche, Takeda, and other companies has resulted in numerous pubHcations and patents describing variations. These routes are convergent, shorter, and of reasonably high throughput. 

The first CO route to make adipic acid is a BASF process employing CO and methanol in a two-step process producing dimethyl adipate [627-93-0] which is then hydroly2ed to the acid (43—46). Cobalt carbonyl catalysts such as Co2(CO)g are used. Palladium catalysts can be used to effect the same reactions at lower pressures (47—49). 

The other CO route for adipic acid manufacture involves 1,4-addition of CO and O2 to butadiene to produce an intermediate, which is subsequently hydrogenated and hydroly2ed to adipic acid (50). This is called the oxycarbonylation process. Both the BASF and the oxycarbonylation processes have been intensively investigated. 

The carbonylation of methanol is currently one of the major routes for acetic acid production. The basic liquid-phase process developed by BASF uses a cobalt catalyst at 250°C and a high pressure of about 70... 

BASF is operating a semicommercial plant for the production of adipic acid via this route.A new route to adipic acid occurs via a sequential carbonylation, isomerization, hydroformylation reactions.The following illustrates these steps ... 

A one-step synthetic route to methine pigments, starting from o-phthalonitrile, has been described by BASF [21],... 

The early days of Copper Phthalocyanine Green synthesis were dominated by two competitive routes. One method was the synthesis of tetraphenyl copper phthalocyanine (Bayer), while the second method involved chlorination of copper phthalocyanine in carbon tetrachloride to form copper tetradeca to hexadeca-chloro phthalocyanine (BASF). It was on the grounds of economical considerations that manufacturers began to prefer the chlorination technique in industrial scale production. 

Other methods for the preparation of acetic acid are partial oxidation of butane, oxidation of ethanal -obtained from Wacker oxidation of ethene-, biooxidation of ethanol for food applications, and we may add the same carbonylation reaction carried out with a cobalt catalyst or an iridium catalyst. The rhodium and iridium catalysts have several distinct advantages over the cobalt catalyst they are much fester and fer more selective. In process terms the higher rate is translated into much lower pressures (the cobalt catalyst is operated by BASF at pressures of 700 bar). For years now the Monsanto process (now owned by BP) has been the most attractive route for the preparation of acetic acid, but in recent years the iridium-based CATTVA process, developed by BP, has come on stream. 

C2 route Ethylene, CO, H2, H2CO Carbonylation of ethylene to BASF... 

BASF led the development of a route based on ethylene and synthesis gas. Its four step process begins with the production of propionaldehyde from ethylene, CO, and H2 using a proprietary catalyst mixture that they aren t telling anything about. Reaction with formaldehyde gives methacrolein. The last two steps are the same as above—oxidation with air yields the MAA subsequent reaction with methanol yields MMA. 

In this connection the reduction of acetic acid to ethanol by Humphreys Glasgow, Davy McKee and BASF must be quoted as an attractive route to ethanol. This route combines the high selectivity of the Monsanto acetic acid process with a hydrogenation step. 

One process that capitalizes on butadiene, synthesis gas, and methanol as raw materials is BASF s two-step hydrocarbonylation route to adipic acid(3-7). The butadiene in the C4 cut from an olefin plant steam cracker is transformed by a two-stage carbonylation with carbon monoxide and methanol into adipic acid dimethyl ester. Hydrolysis converts the diester into adipic acid. BASF is now engineering a 130 million pound per year commercial plant based on this technology(8,9). Technology drawbacks include a requirement for severe pressure (>4500 psig) in the first cobalt catalyzed carbonylation step and dimethyl adipate separation from branched diester isomers formed in the second carbonylation step. 

Ethylene oxide has been produced commercially by two basic routes the ethylene chlorohydrin and direct oxidation processes. The chlorohydrin process was first introduced during World War I in Germany by Badische Anilin-nnd Soda-Fabrik (BASF) and others (95). The process involves the reaction of ethylene with hypochlorous acid followed by dehydrochlorination of the resulting chlorohydrin with lime to produce ethylene oxide and calcium chloride. Union Carbide Corp. was the first to commercialize this process in the United States in 1925. The chlorohydrin process is not economically competitive, and was quickly replaced by the direct oxidation process as the dominant technology. At the present time, all the ethylene oxide production in the world is achieved by the direct oxidation process. 

R,S)-Citronellal can be purchased from BASF, and (R)-citronellal from Dragoco, Fluka, or Takasgo Perfumery Co., Ltd., Japan. (R)-Citronellal can also be synthesized from pulegone with ee >99%.5 (S)-Citronellal may be obtained by oxidation of (S)-citronellol,6 which is accessible by different routes with ee 95%.7 The optical purity of citronellal can be determined by GLC after conversion to the acetal of (-)-(2R,4R)-pentanediol.8 For the reactions described, (R,S)-citronellal from BASF, (R)-citronellal from Dragoco, and (S)-citronellol from Fluka were used. (R,S)-Citronellal... 

In 1992, BASF opened a 35 000 tons per year ibuprofen production plant in Bishop, Texas. This plant was the result of the elegant green chemistry route developed by the BHC consortium. The clean synthesis of ibuprofen is an excellent example of how combining catalysis and green chemistry can yield both commercial success and environmental benefits. Ibuprofen is a nonsteroidal, anti-inflammatory painkiller. It is a popular over-the-counter drug against headache, toothache, and muscular pains. You may know it better as Advil , Motrin , or Nurofen. 

PO was manufactured by the chlorohydrin route first during World War I in Germany by BASF and others. This route (below) involves reaction of propylene with hypochlorous acid followed by treatment of the resulting propylene chlorohydrin with a base such as caustic or lime. The products of the second reaction are PO and sodium or calcium chloride (Fig. 10.22). 

Whereas (S)-metolochlor is produced chemically by asymmetric hydrogenation, a biocatalytic route is employed by BASF for the production of (S)-methoxyisopropylamine on the multithousand-ton scale per annum. Resolution of racemic methoxyisopropy-... 

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