Ether production

Uses. Union Carbide consumes its vinyl ether production in the manufacture of glutaraldehyde [111-30-8J. BASF and GAF consume most of their production as monomers (see Vinyl polymers). In addition to the homopolymers, the copolymer of methyl vinyl ether with maleic anhydride is of particular interest. 

IFP Process for 1-Butene from Ethylene. 1-Butene is widely used as a comonomer in the production of polyethylene, accounting for over 107,000 t in 1992 and 40% of the total comonomer used. About 60% of the 1-butene produced comes from steam cracking and fluid catalytic cracker effluents (10). This 1-butene is typically produced from by-product raffinate from methyl tert-huty ether production. The recovery of 1-butene from these streams is typically expensive and requires the use of large plants to be economical. Institut Francais du Petrole (IFP) has developed and patented the Alphabutol process which produces 1-butene by selectively dimerizing ethylene. 

Liquid mixtures of methanol and hydrochloric acid slowly yield methyl chloride even at 0°C (20,21), The typical process is carried out by contacting the alcohol with hydrochloric acid at 70 to 160°C and 0.1—1 MPa (15—150 psig) in the presence of a catalyst such as zinc chloride, quaternary amines (18,19,22), or with no catalyst at aH (23,24). TypicaHy 0.5 to 3% of the methanol is converted to dimethyl ether. Product methyl chloride is taken out of the reactor as a vapor and is cooled to condense as much of the water vapor and HCl as possible. Dimethyl ether and the residual water is then removed and the finished methyl chloride is condensed. 

The piincipal by-pioducts aie the result of direct chlorine addition to give 1,2-dichlotoptopane [78-87-5] and ether formation. The ether product is dichloropropyl ether [108-60-1] or 2,2 -oxybis(l-chloropropane). 

Ether production from the reaction of monohydric alcohols with linear olefins has also been demonstrated under more severe conditions using a 2eohte-type catalyst system (15). However, it has not been commerciali2ed as yet. 

The unsaturated tetraoxaquaterene (accompanied by linear condensation products) was first synthesized in 18.5% yield by the acid-catalyzed condensation of furan with acetone in the absence of added lithium salts. Other ketones also condensed with furan to give analogous products in 6-12% yield.A corresponding macrocycle was also prepared in 9% yield from pyrrole and cyclohexanone. The macrocyclic ether products have also been obtained by condensation of short linear condensation products having 2, 3, or 4 furan rings with a carbonyl compound. ... 

The MTBE reaction is equilihrium limited. Higher temperatures increase the reaction rate, hut the conversion level is lower. Lower temperatures shift the equilihrium toward ether production, hut more catalyst... 

An amine-terminated poly ether (ATPE) is prepared as follows. Charge poly(tetramethylene oxide) diol (PolyTHF 1000, BASF, 75.96 g, 0.0759 m) to a 500-mL three-neck round-bottom flask fitted with a thermocouple, a mechanical stirrer, and a vacuum port. Add tert-butylacetoacetate (24.04 g, 0.1582 m) and apply vacuum. Heat at 175° C for 4 h, Fourier transform infrared (FTIR) analysis should indicate complete loss of the polyol OH absorption at 3300 cm. The room temperature viscosity of the product should be about 520 mPa-s. React this acetoacetylated product (85.5 g, 0.0649 m) with cyclohexylamine (14.5 g, 0.1465 m) at 110° C under vacuum for several hours. Cool the resultant cyclohexylaminocrotonate poly ether product to room temperature (1790 mPa-s at room temperature). 

This reaction has been also described for low chlorinated dibenzodioxins. Assuming an identical MS response factor for monoBrDD and monobromohydroxy-biphenyl ether (monoBrDPE) a quantification study shows that monoBrDPE is much more stable towards photolysis compared to monoBrDD, because it accumulates in the mixture of the reaction products. For the dibrominated dibenzodioxins the same reaction (ether fission) is observed but to a minor extent. With triBrDD and higher brominated BrDD no diaryl-ether products are observed at all. 

The synthetic preparation of 2,8-dichlorodibenzo-p-dioxin was facilitated in that the chemical precursor, 2,4,4 -trichloro-2 -hydroxydiphenyl ether, was available as a pure material. Condensation was induced by heating the potassium salt at 200 °C for 15 hours in bis (2-ethoxyethyl) ether. Product analysis by GLC and mass spectrometry revealed an unexpected dichlorophenol and a monochlorodibenzo-p-dioxin. Further, the product initially isolated by crystallization from the reaction mixture was 2,7-dichlorodibenzo-p-dioxin, rather than the expected 2,8-isomer. Cooling of the mother liquor yielded crystalline plates which were shown to be 2,8-dichlorodibenzo-p-dioxin by x-ray diffraction (Reaction 2). 

A recently developed application of the Ramberg-Backlund reaction is the synthesis of C-glycosides. The required thioethers can be prepared easily by exchange with a thiol. The application of the Ramberg-Backlund conditions then leads to an exocyclic vinyl ether that can be reduced to the C-nucleoside.95 Entries 3 and 4 in Scheme 10.6 are examples. The vinyl ether group can also be transformed in other ways. In the synthesis of partial structures of the antibiotic altromycin, the vinyl ether product was subjected to diastereoselective hydroboration. 

When alcohols are added to the reaction mixture, unsymmetrical ether products may be obtained. Starting with a mixture of aldehydes can also give rise to the formation of unsymmetrical ethers. These ether products are formed under conditions different from those used in the formation of ethers directly from alcohols. Thus, it is postulated that the reaction sequence that leads from the carbonyl substrate to the ether involves the intermediate formation of hemiacetals, acetals, or their protonated forms and alkoxycarbenium ions, which are intercepted and reduced to the final ether products by the organosilicon hydrides present in the reaction mix. The probable mechanistic scheme that is followed when Brpnsted acids are present is outlined in Scheme 2.311-327 328... 

The PhSiH3/RhCl(PPh3)3 combination reduces trimethyl orthobenzoate to the dimethyl acetal of benzaldehyde with small amounts of methyl benzyl ether product (Eq. 315) 493... 

The Alder-ene cyclization of allylic silyl ethers represents a clever use of cycloisomerization chemistry, as the enol ether products can be easily unmasked to yield aldehydes. Palladium-catalyzed cycloisomerization of 1,6- and 1,7-enynes containing an allylic oxygen most often gives rise to 1,3-dienes (see Section 10.12.4.1). However, enynes of type 63 underwent facile Alder-ene cyclization to the corresponding five- or six-membered rings (Equation (40)) using both [CpRu(MeCN)3]PF6 41 and the Cp analog ([Cp Ru(MeCN)3]PF6, 64).53... 

Not surprisingly, the cobalt-complexed ether products obtained by the Nicholas reaction can be subjected directly to the Pauson-Khand sequence (Scheme 7).244... 

Isopropanolamines, 20 795, 812 2-Isopropanol-water system, evolving separation strategies for, 22 322-325. See also Water- IPA-hexane system Isopropenyl acetate, 7 148 74 596 m-Isopropenyl-a,a-dimethylbenzyl isocyanate (TMI), 25 463 Isopropenyl methyl ether, production from acetone, 7 163... 

Attempted preparation of the aldehyde precursor of the five-membered ether product through oxidation of the corresponding alcohol led not to the aldehyde, but instead the cyclic ether itself (Eq. 9.104). Evidently the cyclization reaction is facile in this case. 

The isomeric propargylic stannylated aldehyde intermediate, on the other hand, could be prepared from the alcohol precursor without competing cyclization to an seven-membered enol ether product (Eq. 9.105). Treatment of this stannane with SnCl4 afforded the cis-disubstituted tetrahydrofuran stereoselectively. Presumably, this reaction proceeds through an allenyl trichlorostannane intermediate. 

Both the halide and hydride etherate products of Eqs. (5) and (6) can be easily desolvated by heating to ca 90-120°C under reduced pressure [Eq. (7)]. The halide and hydride... 

With the use of NMR spectroscopy Giering and coworkers studied the reaction of acetophenone and HSiBu3 in more detail. The catalyst was [(1,5-cod)RhCl]2 and R-BINAP [36], They noted that the silyl enol ether by-product was formed mainly at the beginning of the reaction and thus this must form via an independent pathway. The common intermediate for silyl ether product and... 

The formation of byproduct methyl benzyl ether was the key reason for the low selectivity to ester in the absence of alumina. A more careful examination of the product distributions with time was made using the alkoxide, alkoxide on alumina and bicarbonate on alumina bases. The results from Table V indicate that the formation of ether was indeed the predominant pathway with alkoxide alone, while the presence of alumina retarded this conversion and promoted the carboxyalkylation pathway. The bicarbonate on alumina gave little ether product and excellent selectivity to the methyl phenylacetate. 

Complexation of [Cp IrCl2]2 with iV-heterocyclic carbenes has led to complexes such as 25, developed by Peris and coworkers [107, 108], and 133, developed by Crabtree and coworkers [12]. Complex 24 is activated by the addition of silver triflate and is effective for the iV-alkylation of amines with alcohols and for the iV-alkylation of anilines with primary amines. Complex 25 has also been shown to couple benzyl alcohol 15 with a range of alcohols, including ethanol 134, to give ether products such as ether 135 (Scheme 31). Complex 133 was an active hydrogen transfer catalyst for the reduction of ketones and imines, using 2-propanol as the hydrogen source. It was also an effective catalyst for the iV-alkylation of amines... 

Carreira et al. reported the kinetic resolution of branched allylic carbonates catalyzed by an iridium complex derived from a chiral [2.2.2]-bicyclooctadiene [48]. Reactions of allylic carbonates with phenol were run to 50% conversion of the carbonate, leaving unreacted allylic carbonate in high enantiomeric excess (Scheme 32). The phenyl ether products were also isolated in mid-to-high enantiomeric excess. 

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