Propylene oxide, adduct

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). 

Diaminopropane Processes. 1,2-Propylenediamine can be produced by the reductive amination of propylene oxide (142), 1,2-propylene glycol [57-55-6] (143), or monoisopropanolamine [78-96-6] (144). 1,3-Propanediol [504-63-2] can be used to make 1,3-diaminopropane (143). Various propaneamines are produced by reducing the appropriate acrylonitrile—amine adducts (145—147). Polypropaneamines can be obtained by the oligomerization of 1,3-diaminopropane (148,149). 

Both ethylene and propylene oxide have been used in the preparation of adducts from a variety of amines, including ethylene diamine and diethylene triamine. The latter amine provides adducts which appetu" free of skin sensitising effects. 

A way to anh-configurated a-amino-/ -hydroxycarboxylic acids is opened by the aldol addition of oxazolidine amides 7a and 7b. The method1061 is illustrated by a synthesis of (2R,3R)-p-hydroxyleucine (9) which is available from the major diastereomeric adduct 8 (d.r. 92 8) upon successive treatment with 1 N HC1 (30 min). 5 N HCl (100 C, 12 h), and propylene oxide (reflux in ethanol, 30 min). 

Phosphoric acid esters based on alkylene oxide adducts are of great interest. Their properties can be altered by the length and structure of the hydrophobic alkyl chain. But they are also controlled by the kind and length of the hydrophilic alkyleneoxide chain. The latter can easily be tailored by selection between ethylene oxide and propylene oxide and by the degree of alkoxylation. 

Triols. One triol used was the propylene oxide adduct of 1,2,6-hexanetriol, designated LHT-240 and supplied by Union Carbide Chemicals Company. After degassing, its hydroxyl, unsaturation, and water contents were 4.31 meq/g, <0.01 meq/g, and 0.004%, respectively. Thus, the material was essentially trifunctional, and its number average molecular weight was 696. If the unsaturation was exactly 0.01 meq/g, then the number-average functionality was 2.99. 

This can be understood in terms of solvation effects. Cellulose is substituted in order to disrupt hydrogen bonding among the glucopyranosyl hydroxyl groups adducts such as ethylene or propylene oxide do not increase the hydrophilicity of the... 

This is a very important group of products and most of them are adducts of long-chain alcohols or alkylphenols with a number of ethylene oxide (EO) units. Adducts with propylene oxide (PO) and copolymers of ethylene and PO are also used although they are less important in terms of usage volume than the pure ethoxylate derivatives. 

Closure of the seventh ring was effected by treatment of 121 with 4.68 equiv of PdC and 3.1 equiv of AgBF4 [58] in acetonitrile containing propylene oxide as an acid scavenger. The incipient heptacyclic a-pallladium adduct was worked up immediately by the addition of the ethanol and NaBHjto afford the desired indole 122. 

A mixture of the alkylated adducts 39 and 1.5M HC1 (15-20mL-mmol ) was heated to reflux for 2-8h until hydrolysis was complete, as determined by 31P NMR. The mixture was concentrated in vacuo, the residue was dissolved in H20, and the soln was washed with Et20 and reconcentrated in vacuo. The product was finally purified by ion-exchange chromatography or by dissolution in hot EtOH (twice the minimum volume required) followed by cooling to rt and precipitation of the zwitterion by the addition of propylene oxide. The 1-aminoalkylphosphinic acids 33 were isolated as white solids. 

Meriting special comment on account of certain recent findings is the reagent o-aminothiophenol. This substance was reported, first in J 949 and again on several subsequent occasions,2 Bl B to yield 3.3-dihydrophenothiazine on condensation with ethylene oxide in base, Mid the corresponding substituted 2,3-dihydrophenothiazines with propylene oxide, cyclohexene oxide, and styrene oxido respectively. It Las now been established, however, in three laboratories,5 M that previous reports were in error. The products formed are in fact normal open-chain adducts, aa shown in Eqa. (670)-<672). Styrene... 

Unaymmetrical epoxides were said to give rise to mixed products, although experimental details were not included. Eqs. (908) and (900) illustrate the action of diethyl phosphite in base on propylene oxide mid isobutylene oxide. The latter undergoes preliminary isomerisation to wobutyrsddehyde before yielding a conventional carbonyl adduct. 

Propylene oxide was found to react at each of its terminals, yielding a mixture of isomeric chlorohydrina on methanolyais of the boron containing adducts/ On the other hand, epichlorohydrin gave otilv 1,3-diohloro-2-propanol on similar treatment, indicating exclusive attack on the terminal epoxide carbon atom (Eq, 060). 

Propylene Oxide Adducts. SAE, in general, have better foam breakability among the nonionics, presumably due to the secondary alkyl structure and narrow distribution of EO chain lengths. Besides, modification of nonionics by the addition of propylene oxide (PO) to the terminal hydroxyl group generally reduces the foaming capacity(30). The addition of PO to SAE may, therefore, lead to nonionics with low and fast breakable foams. 

Figure 32. Foam properties of propylene oxide adduct of secondary alcohol ethoxylate compared with those of others. Test conditions method—Ross-Miles (JIS-K-3362) surfactant concentration—1.0 wt % water temperature—25°C. ((- -) Cn.H SAE (7EO) + (4.5PO) (-1-) CI2 + Ii PAE (7EO) + (4.5PO) (-U-) HPE (8EO) + (4.5PO))...

Su, Borho and Xu have applied rotational spectroscopic and high-level ab initio studies to the 1 1 chiral molecular adduct of propylene oxide dimer [117], Six homochiral and six heterochiral conformers were predicted to be the most stable configurations where each monomer acts as a proton acceptor and a donor simultaneously, forming two 6- or 5-membered intermolecular hydrogen-bonded rings. Rotational spectra of six, that is, three homochiral and heterochiral conformer pairs, out of the eight conformers that were predicted to have sufficiently large permanent electric dipole moments were measured and analyzed. 

The first report on the coordination polymerisation of epoxide, leading to a stereoregular (isotactic) polymer, concerned the polymerisation of propylene oxide in the presence of a ferric chloride-propylene oxide catalyst the respective patent appeared in 1955 [13]. In this catalyst, which is referred to as the Pruitt Baggett adduct of the general formula Cl(C3H60)vFe(Cl)(0C3H6),CI, two substituents of the alcoholate type formed by the addition of propylene oxide to Fe Cl bonds and one chlorine atom at the iron atom are present [14]. A few years later, various types of catalyst effective for stereoselective polymerisation of propylene oxide were found and developed aluminium isopropoxide-zinc chloride [15], dialkylzinc-water [16], dialkylzinc alcohol [16], trialkylalumi-nium water [17] and trialkylaluminium-water acetylacetone [18] and trialkyla-luminium lanthanide triacetylacetonate H20 [19]. Other important catalysts for the stereoselective polymerisation of propylene oxide, such as bimetallic /1-oxoalkoxides of the [(R0)2A10]2Zn type, were obtained by condensation of zinc acetate with aluminium isopropoxide in a 1 2 molar ratio of reactants [20-22]. 

Ethylene and Propylene Oxide Amine Adducts. Polyamines, such as DETA, react readily with ethylene oxide in the presence of water to yield mono- or dihydroxyalkyl derivatives, depending on the ratio of reactants. As the extent of the reaction progresses, the resulting... 

FIGURE 5.4 Ethylene and propylene oxide adducts of amines. 

Su Z, Wen Q, Xu Y (2006) Conformational stability of the propylene oxide-water adduct direct spectroscopic detection of O-H... 0 hydrogen bonded conformers. J Am Chem Soc 128 6755-6760... 

To this liquid mixture was added a mixture of 50 parts by weight (0.473 equivalent) of a polyol of equivalent weight 105.6 (the adduct of propylene oxide and a mixture of polyamines containing 50% by weight of methylenedianiline obtained by the acid condensation of aniline and formaldehyde) 50 parts by weight of dimethyl sulfoxide and 10 parts by weight of a silicone surfactant. 

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