Carbamate process

Inorganic bases have been also employed in this system. When Butcher first used alkali carbonates [50], it was reported that, in DMF and at ambient temperature, the carbamation of primary and secondary aliphatic amines (or also arylamines) with alkyl halides under a C02 atmosphere (0.1 MPa) was effectively promoted by Cs2C03 [50, 51]. The Cs+ cations in the solvent used (DMF) did not form ion pairs with counterions, and favored the formation of naked carbamate anions that were more reactive at the O-ends with alkyl halides. Jung further found that the addition of tetrabutylammonium iodide (TBAI) to the system RR NH/ C02/RX/Cs2C03/DMF promoted the carbamation process with a higher yield and selectivity with respect to N-alkylation [51]. The process has been successfully extended to the synthesis of carbamate functionalities on solid phases. In this case, resin-bound carbamates are readily released from the resin by treatment with LiAlH4 in THF, yielding the respective N-methyl secondary amines [51]. 

The carbamate process, which uses urea as a modifying agent, represents a greener alternative to the xanthate process (Ekman el al., 1984). However, the industrial scale-up has not yet been successful. 

Alternatives to alkaline solutions of carbon disulfide are combinations of formaldehyde and DMSO various alkyl silanes, and urea and alkali. The latter is currently being promoted for industrial applications. It is known under the term carbamate process. The carbamate process has advantages over the viscose rayon process while being able to use the same process technology. 

Although the new technology is more expensive, it can be expected that this environmentally friendly carbamate process will find wider commercial success in the near future. 

One common feature of the viscose, euprammonium, and carbamate processes is the chemically modified cellulose is regenerated into cellulose after the extrusion. Fibers made from these processes often are called rayon fibers. However, useful fibers can be produced by derivative methods without the regeneration of cellulose. Two important examples are cellulose acetate and cellulose triacetate fibers. Cellulose acetate can be obtained by aeetylation of cellulose with acetic acid and acetic anhydride with sulfuric acid as a catalyst. Cellulose triacetate, which is partly saponified to get the desired degree of substitution, is produced by a similar process. Both cellulose acetate and cellulose triacetate keep their derivative structure in final fibers. The major difference between these two fibers is that in cellulose acetate fibers, less than 92% but at least 74% of the -OH groups are acetylated, but in triacetate fibers, at least 92% of the hydroxyl groups are acetylated. 

Carbamates such as Aldicarb undergo degradation under both aerobic and anaerobic conditions. Indeed the oxidation of the sulfur moiety to the sulfoxide and sulfone is part of the activation of the compound to its most potent form. Subsequent aerobic metaboHsm can completely mineralize the compound, although this process is usually relatively slow so that it is an effective iasecticide, acaricide and nematocide. Anaerobically these compounds are hydrolyzed, and then mineralized by methanogens (61). 

The stripper off-gas going to the high pressure carbamate condensers also contains the carbamate recovered in the medium and low pressure recirculation sections. Both of these systems ate similar to those shown in the total-recycle process. 

The Stainicaibon process is described in Figures 3—7. The synthesis section of the plant consists of the reactor, stripper, high pressure carbamate condenser, and a high pressure reactor off-gas scmbber. In order to obtain a maximum urea yield pet pass through the reactor, a pressure of 14 MPa (140 bar) and a 2.95/1 NH —CO2 molar ratio is maintained. The reactor effluent is distributed over the stripper tubes (falling-film type shell and tube exchanger) and contacted by the CO2, countercurrendy. This causes the partial NH pressure to decrease and the carbamate to decompose. 

Toyo Engineering-AGES Process. The synthesis section of the ACES process (Fig. 8) consists of a reactor, a stripper, two carbamate condensers, a scmbber and operates at 17.5 MPa (175 bars). The reactor is operated at 190°C with a NH /CO2 ratio of 4.0 (mol/mol). Liquid NH is fed directly into the reactor by a centrifugal ammonia pump. Gaseous CO2 is sent from the centrifugal CO2 compressor to the bottom section of the falling-film type stripper. 

Because an excess of ammonia is fed to the reactor, and because the reactions ate reversible, ammonia and carbon dioxide exit the reactor along with the carbamate and urea. Several process variations have been developed to deal with the efficiency of the conversion and with serious corrosion problems. The three main types of ammonia handling ate once through, partial recycle, and total recycle. Urea plants having capacity up to 1800 t/d ate available. Most advances have dealt with reduction of energy requirements in the total recycle process. The economics of urea production ate most strongly influenced by the cost of the taw material ammonia. When the ammonia cost is representative of production cost in a new plant it can amount to more than 50% of urea cost. 

Neste patented an industrial route to a cellulose carbamate pulp (90) which was stable enough to be shipped into rayon plants for dissolution as if it were xanthate. The carbamate solution could be spun into sulfuric acid or sodium carbonate solutions, to give fibers which when completely regenerated had similar properties to viscose rayon. When incompletely regenerated they were sufficientiy self-bonding for use in papermaking. The process was said to be cheaper than the viscose route and to have a lower environmental impact (91). It has not been commercialized, so no confirmation of its potential is yet available. 

Second-generation juvenoids incorporate more substantial stmctural departures from neotenin and are more resistant to metaboHc and environmental degradation. Epiphenonane, 2-ethyl-3-[3-ethyl-5-(4-ethylphenoxy)-pent-3-en-yl] 2-methyloxirane (131), has a rat oral LD q of 4000 mg/kg. It and similar juvenoids are used in China and Japan to prolong the last larval instar of the silkworm so that silk production is increased 10—15%. Fenoxycarb, ethyl [2-(4-phenoxyphenoxy)ethyl] carbamate (132) (mp 53°C, vp 0.0078 mPa at 20°C), is soluble in water to 6 mg/L. The rat oral LD q is >16,800 mg/kg. Fenoxycarb has a wide spectmm of activity, interfering with the developmental processes of fleas, cockroaches, and ants. 

A simpler nonphosgene process for the manufacture of isocyanates consists of the reaction of amines with carbon dioxide in the presence of an aprotic organic solvent and a nitrogeneous base. The corresponding ammonium carbamate is treated with a dehydrating agent. This concept has been apphed to the synthesis of aromatic and aUphatic isocyanates. The process rehes on the facile formation of amine—carbon dioxide salts using acid haUdes such as phosphoryl chloride [10025-87-3] and thionyl chloride [7719-09-7] (30). 

This simple reaction is the bedrock of the polyurethane iadustry (see Urethane polymers). Detailed descriptions of the chemistry and process have been published (65—67). Certain carbamates are known to reversibly yield the isocyanate and polyol upon heating. This fact has been commercially used to synthesize a number of blocked isocyanates for elastomer and coating appHcations. 

Attempts have been made to develop methods for the production of aromatic isocyanates without the use of phosgene. None of these processes is currently in commercial use. Processes based on the reaction of carbon monoxide with aromatic nitro compounds have been examined extensively (23,27,76). The reductive carbonylation of 2,4-dinitrotoluene [121 -14-2] to toluene 2,4-diaLkylcarbamates is reported to occur in high yield at reaction temperatures of 140—180°C under 6900 kPa (1000 psi) of carbon monoxide. The resultant carbamate product distribution is noted to be a strong function of the alcohol used. Mitsui-Toatsu and Arco have disclosed a two-step reductive carbonylation process based on a cost effective selenium catalyst (22,23). 

Naphthol is mainly used in the manufacture of the insecticide carbaryl (59), l-naphthyl A/-methyicarbamate/ iJ-2j5 - (Sevin) (22), which is produced by the reaction of 1-naphthol with methyl isocyanate. Methyl isocyanate is usually prepared by treating methylamine with phosgene. Methyl isocyanate is a very toxic Hquid, boiling at 38°C, and should not be stored for long periods of time (Bhopal accident, India). India has developed a process for the preparation of aryl esters of A/-alkyl carbamic acids. Thus l-naphthyl methylcarbamate is prepared by refluxing 1-naphthol with ethyl methylcarbamate and POCl in toluene (60). In 1992, carbaryl production totaled > 11.4 x 10 t(35). Rhc ne-Poulenc, at its Institute, W. Va., facihty is the only carbaryl producer in United States. 

Starch is subject to fermentation by many microorganisms and, unless the mud is saturated with salt or the pH is >11.5, a preservative or biocide must be added if the mud is to be used for an extended period of time. The most common biocide until the mid-1980s was paraformaldehyde [9002-81-7]. This material has been largely replaced by isothia2olones (at 5—10 ppm cone) (74), carbamates, and glutaraldehyde [111-30-8]. Alternatively, the biocide may be incorporated during the processing of the starch and is present in the commercial product. 

Enzymatic Method. L-Amino acids can be produced by the enzymatic hydrolysis of chemically synthesized DL-amino acids or derivatives such as esters, hydantoins, carbamates, amides, and acylates (24). The enzyme which hydrolyzes the L-isomer specifically has been found in microbial sources. The resulting L-amino acid is isolated through routine chemical or physical processes. The D-isomer which remains unchanged is racemized chemically or enzymatically and the process is recycled. Conversely, enzymes which act specifically on D-isomers have been found. Thus various D-amino acids have been... 

Final Purification. Oxygen containing compounds (CO, CO2, H2O) poison the ammonia synthesis catalyst and must be effectively removed or converted to inert species before entering the synthesis loop. Additionally, the presence of carbon dioxide in the synthesis gas can lead to the formation of ammonium carbamate, which can cause fouHng and stress-corrosion cracking in the compressor. Most plants use methanation to convert carbon oxides to methane. Cryogenic processes that are suitable for purification of synthesis gas have also been developed. 

Distillers employ a somewhat unique process to make various products and have tailored approaches to control and reduce ethyl carbamate to their own particular process. Some of the methods used are the use of copper packing in the rectifying section of stills, increased frequency of cleaning stills and other equipment, and using a cool-down period in the cleaning procedure. Increased rectification also reduces ethyl carbamate. Keeping the system clean is critical to minimising ethyl carbamate. 

Simple amides that are difficult to cleave can first be converted to a BOC derivative by an exchange process that relies on the reduced electrophilicity of the carbamate as well as its increased steric bulk. °... 

The common impurities found in amines are nitro compounds (if prepared by reduction), the corresponding halides (if prepared from them) and the corresponding carbamate salts. Amines are dissolved in aqueous acid, the pH of the solution being at least three units below the pKg value of the base to ensure almost complete formation of the cation. They are extracted with diethyl ether to remove neutral impurities and to decompose the carbamate salts. The solution is then made strongly alkaline and the amines that separate are extracted into a suitable solvent (ether or toluene) or steam distilled. The latter process removes coloured impurities. Note that chloroform cannot be used as a solvent for primary amines because, in the presence of alkali, poisonous carbylamines (isocyanides) are formed. However, chloroform is a useful solvent for the extraction of heterocyclic bases. In this case it has the added advantage that while the extract is being freed from the chloroform most of the moisture is removed with the solvent. 

Only one melamine molecule is formed from six urea molecules, whilst three molecules of ammonia carbamate are formed. Whilst this can be recycled to urea the conversion from urea to melamine per cycle is at most 35%. Both the main route and the recycling operation involve high pressures and the low process efficiency offsets some of the apparent economic attractions of the route compared to those from dicy . 

Initially, the water slowly reacts with the isocyanate. However, the reaction can be catalyzed with an appropriate catalyst, such as dibutyltin dilaurate or a morpholine tertiary amine catalyst. The isocyanate will react with water to form a carbamic acid, which is unstable and splits off carbon dioxide, to produce a terminal amine end group (see p. 76 in [6]). This amine then reacts with more isocyanate-terminated prepolymer, as shown above, to form a polyurea. This process repeats itself, building up molecular weight and curing to become a polyurea-polyurethane adhesive. 

The insecticide carbaryl can be produced by several routes, some of which do not use methyl isocyanate, or which generate only small quantities of this toxic material as an in-process intermediate (Kletz, 1991b). One company has developed a proprietary process for manufacture of carbamate insecticides which generates methyl isocyanate as an in-situ intermediate. Total methyl isocyanate inventory in the process is no more than 10 kilograms (Kharbanda and Stallworthy, 1988 Manzer, 1994). 

The main difference between tlie various urea syntliesis processes are in tlie metliods used to handle tlie converter effluent, to decompose the carbamate and carbonate, to recover tlie urea, and to recover tlie mireacted aimnonia and carbon dioxide for recycle with a nia. inium recovery of heat. The amiutil production rate is approximately 4.5 million metric tons. End use is... 

The second reaction represents the decomposition of the carbamate. The reaction conditions are 200°C and 30 atmospheres. Decomposition in presence of excess ammonia limits corrosion problems and inhibits the decomposition of the carbamate to ammonia and carbon dioxide. The urea solution leaving the carbamate decomposer is expanded by heating at low pressures and ammonia recycled. The resultant solution is further concentrated to a melt, which is then prilled by passing it through special sprays in an air stream. Figure 5-3 shows the Snamprogetti process for urea production. ... 

---