With ethylene oxide

Trimethylamine, CjH N, (CH3J3N. Colourless liquid with a strong fishy odour, miscible with water, m.p. — I24 C, b.p. 3-5°C. It occurs naturally in plants, herring brine, bone oil and urine. It reacts with hydrogen peroxide to give trimethylamine oxide and with ethylene oxide to give choline its commercial importance stems chiefly from this latter reaction. 

Me3CCH2CMe2C H40H. M.p. 8l-83"C, b.p. 286-288°C. Made by alkylation of phenol. Forms oil-soluble resins with methanal (salts used as oil additives) and surfactants (with ethylene oxide). 

In contrast to alkylations with most of the alkyl halides, the reactions of anions with ethylene oxide in organic solvents such as diethyl ether and THE... 

Note I. A solution of 1-1ithiomethoxyal1ene, prepared from methoxyallene and BuLi-hexane-THF, did not react with ethylene oxide below 20°C. The reaction started at about 30°C, but the reaction mixture became very dark. 

The reaction of lithiated cumulenic ethers with ethylene oxide, trimethyl-chlorosilane and carbonyl compounds shows the same regiosnecificity as does the alkylation. 

Lithiated indoles can be alkylated with primary or allylic halides and they react with aldehydes and ketones by addition to give hydroxyalkyl derivatives. Table 10.1 gives some examples of such reactions. Entry 13 is an example of a reaction with ethylene oxide which introduces a 2-(2-hydroxyethyl) substituent. Entries 14 and 15 illustrate cases of addition to aromatic ketones in which dehydration occurs during the course of the reaction. It is likely that this process occurs through intramolecular transfer of the phenylsulfonyl group. 

Reactions of the 2-amino-4,5-substituted thiazole (52) in acetic acid with ethylene oxide has been reported to give the N-exocyclic disubstitution product (S3) (201) in a 40% yield (Scheme 38). The reactive species in this reaction is probably the carbocation generated in acetic acid by ethvlene oxide. 

Grignard reagents react with ethylene oxide to yield primary alcohols containing two more carbon atoms than the alkyl halide from which the organometallic compound was prepared... 

Section 15 4 Grignard and organolithium reagents react with ethylene oxide to give primary alcohols... 

We saw an example of nucleophilic ring opening of epoxides in Section 15 4 where the reaction of Grignard reagents with ethylene oxide was described as a synthetic route to primary alcohols... 

Chemical Structure and Properties. Homopolymer consists exclusively of repeating oxymethylene units. The copolymer contains alkyhdene units (eg, ethyUdene —CH2—CH2—) randomly distributed along the chain. A variety of end groups may be present in the polymers. Both homopolymer and copolymer may have alkoxy, especially methoxy (CH3 O—), or formate (HCOO—) end groups. Copolymer made with ethylene oxide has 2-hydroxyethoxy end groups. Homopolymer generally has acetate end groups. 

Uses. Most butynediol produced is consumed by the manufacturers in manufacture of butanediol and butenediol. Smak amounts are converted to ethers with ethylene oxide. 

Other interesting perfluoro ether stmctures can be obtained by copolymerization of hexafluoroacetone with ethylene oxide, propylene oxide, and trimethylene oxide with subsequent fluorination to yield the following stmctures (67) ... 

Polysorha.tes. Polyoxyethylene sorbitan esters [9005-63-4] are formed from the reaction of sorbitol esters with ethylene oxide. These emulsifiers are almost always employed in combination with sorbitan esters and are used in the same appHcations (36). 

Urethane Polymers. An important use for glycerol is as the fundamental building block ia polyethers for urethane polymers (qv). In this use it is the initiator to which propylene oxide, alone or with ethylene oxide, is added to produce ttifunctional polymers which, on reaction with diisocyanates, produce flexible urethane foams. Glycerol-based polyethers (qv) have found some use, too, ia rigid urethane foams. 

The various fumigants often exhibit considerable specificity toward insect pests, as shown in Table 8. The proper choice for any control operation is determined not only by the effectiveness of the gas but by cost safety to humans, animals, and plants flammabdity penetratabdity effect on seed germination and reactivity with furnishings. The fumigants may be used individually or in combination. Carbon tetrachloride has been incorporated with carbon disulfide, ethylene dichloride, or ethylene dibromide to decrease flammability, and carbon dioxide is used with ethylene oxide for the same purpose. 

Poly(propylene oxide) [25322-69-4] may be abbreviated PPO and copolymers of PO and ethylene oxide (EO) are referred to as EOPO. Diol poly(propylene oxide) is commonly referred to by the common name poly(propylene glycol) (PPG). Propylene oxide [75-56-9] and poly(propylene oxide) and its copolymers, with ethylene oxide, have by far the largest volume and importance in the polyurethane (PUR) and surfactant industry compared to all other polyepoxides. Articles reviewing propylene oxide (1), poly(propylene oxide) (2—4), other poly(aIkylene oxides) (4), and polyurethanes (5—7) are cited to lead the interested reader to additional detail not in the scope of this article. 

Etherification. Many of the mono alkylphenols and some of the dialkylphenols are converted into ethoxylates which find commercial apphcation as nonionic surfactants (9). For example, -nonylphenol reacts with ethylene oxide under mild basic conditions. 

The major use of 4-cumylphenol is as a chain terminator for polycarbonates. Its use in place of phenol gives a polycarbonate with superior properties (33). Eor a low molecular weight polycarbonate used for injection-molding appHcations, the use of 4-cumylphenol as a chain terminator significantly lowers the volatiHty of the resin. Other uses of 4-cumylphenol include the production of phenoHc resins, some of which have appHcations in the electronics industry (34). Another appHcation of 4-cumylphenol involves its reaction with ethylene oxide to form a specialty surfactant. 

High purity 4-dodecylphenol is used to produce specialty surfactants by its reaction with ethylene oxide. The low color of high purity 4-dodecylphenol is important in this appHcation from a standpoint of aesthetics. 4-Dodecylphenol is also used to produce phenoHc resins which are used in adhesive appHcations and printing inks. 4-Dodecylphenol is also used as an epoxy curing catalyst where the addition of 4-dodecylphenol accelerates curing of the epoxy resin to a hard, nontacky soHd. 

The only significant use for di-j -butylphenol is a specialty nonionic surfactant produced by reaction with ethylene oxide under base catalysis. This surfactant is registered with EPA for use in emulsifying agrochemicals (see Table 3). 

Another subclass of substituted amides that is of great commercial value is the ethoxylated amides. They can be synthesized from alkanolamides by chain extending with ethylene or propylene oxide or by ethoxylation directly from the primary amide (46—48). It was originally beheved that the stepwise addition of ethylene oxide (EO) would produce the monoethano1 amide and then the diethanolamide when sufficient ethylene oxide was added (49), but it has been discovered that only one hydrogen of the amide is substituted with ethylene oxide (50—53). As is typical of most ethylene oxide adducts, a wide distribution of polyethylene oxide chain length is seen as more EO is added. A catalyst is necessary to add ethylene oxide or propylene oxide to a primary or an ethoxylated amide or to ethoxylate a diethoxy alkanolamide synthesized from diethanolamine (54). 

Fats, Oils, or Fatty Acids. The primary products produced direcdy from fats, oils, or fatty acids without a nitrile iatermediate are the quatemized amidoamines, imidazolines, and ethoxylated derivatives (Fig. 3). Reaction of fatty acids or tallow with various polyamines produces the iatermediate dialkylarnidoarnine. By controlling reaction conditions, dehydration can be continued until the imidazoline is produced. Quaternaries are produced from both amidoamines and imidazolines by reaction with methyl chloride or dimethyl sulfate. The amidoamines can also react with ethylene oxide (qv) to produce ethoxylated amidoamines which are then quaternized. 

Epichlorohydrin. Commercial polyester elastomers include both the homopolymer and the copolymer of epichl orohydrin with ethylene oxide. The very polar chloromethyl groups create basic resistance to oil for these polymers, and they have been extensively used in fuel lines however, the desire for lower fuel permeation is causing a search to be made for other polymers (10) (see Elastomers, synthetic-polyethers). 

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