Epoxides with

Amines also react with epoxides at the less substituted carbon atom. As a slightly more testing problem, suggest a synthesis of the alcohol (TM 165) whose derivatives are used in disinfectants ("phemeiide" etc.). 

Primary and secondary amines also react with epoxides (or in situ produced episulfides )r aziridines)to /J-hydroxyamines (or /J-mercaptoamines or 1,2-diamines). The Michael type iddition of amines to activated C—C double bonds is also a useful synthetic reaction. Rnally unines react readily with. carbonyl compounds to form imines and enamines and with carbo-tylic acid chlorides or esters to give amides which can be reduced to amines with LiAlH (p. Ilf.). All these reactions are often applied in synthesis to produce polycyclic alkaloids with itrogen bridgeheads (J.W. Huffman, 1967) G. Stork, 1963 S.S. Klioze, 1975). 

Epoxides and aziridines are also capable of electrophilic subsitution of indoles. Indolylmagncsium bromide and cyclohexene oxide react to give 3-(lrans-2-hydroxycyclohexyl)indole[14]. Reaction of indoles with epoxides also occurs in the presence of Lewis acids. For example, indole reacts with methyl 2S,3R-epoxybutanoate at C3 with inversion of configuration[15]. 

Organolithium reagents react with epoxides in a similar manner... 

This kind of chemical reactivity of epoxides is rather general Nucleophiles other than Gng nard reagents react with epoxides and epoxides more elaborate than ethylene oxide may be used All these features of epoxide chemistry will be discussed m Sections 16 11-16 13... 

The reaction of Grignard reagents with epoxides is regioselective m the same sense Attack occurs at the less substituted carbon of the ring... 

Nucleophilic ring opening of epoxides by ammonia (Section 16 12) The strained ring of an epoxide is opened on nucleo philic attack by ammonia and amines to give 3 ammo alcohols Azide ion also re acts with epoxides the products are p azido alcohols... 

Ethyleneimine reacts with epoxides to form hydroxyaLkylated products, eg, A/-(P-hydroxyethyla2iridine) [1072-52-2]. The epoxide component is frequentiy used in substoichiometric amount in order to prevent multiple aLkoxylation (180—190). Ethyleneimine and episulftdes react to give complex product mixtures, since the l-(2-mercaptoethyl)a2iridine produced initially can easily react further with both reactants (191,192). 

AH of the amine hydrogens are replaced when MDA or PMDA reacts with epoxides to form amine based polyols. These polyols can be used in reactions with isocyanates to form urethanes or with additional epoxide to form cross-linked thermo set resins. 

Until the mid-1960s, phenylenediamines were used primarily for oxidative purposes the para isomer was of major importance. Since then, the use of phenylenediamines to manufacture polymers has far exceeded their use for oxidative purposes. The y -phenylenediamines, (2,4 and 2,6)-toluenediamine, are widely used for the manufacture of polyurethanes. Phenylenediamines are dihinctional and react with other dihinctional compounds, such as dianhydrides, diacyl chlorides, dicarboxyHc acids, and disulfonyl chlorides to give polyamides. Phenylenediamines also give polymers with epoxides, diols, diacetals. 

Some cleavage takes place even if the phenoHc hydroxyl is blocked as an ether link to another phenylpropane unit and quinonemethide formation is prevented. If the a- or y-carbon hydroxyl is free, alkaH-catalyzed neighboring-group attack can take place with epoxide formation and P-aryloxide elimination. In other reactions, blocked phenoHc units are degraded if an a-carbonyl group is present. 

It also reacts with epoxides forming 2-hydroxyalkyl thiols, eg, 2-mercaptoethanol [60-24-2] and bis(2-hydroxyalkyl) sulfides such as bis (2-hydroxyethyl) sulfide [111-48-8], both products are made commercially ... 

P-Ghloroalkoxy Titanates. The reaction of TiCl with epoxides, such as ethylene or propylene oxide (qv), gives P-chloroalkyl titanates (8,9). One example is Ti(OCH2CH2Cl)4 [19600-95-5]. The P-chloroalkoxy titanates can be used to biad refractory powders and ia admixture with diethanolamine to impart thixotropy to emulsion paints (10). 

All lene Oxides and Aziridines. Alkyleneamines react readily with epoxides, such as ethylene oxide [75-21-8] (EO) or propylene oxide [75-56-9] (PO), to form mixtures of hydroxyalkyl derivatives. Product distribution is controlled by the amine to epoxide mole ratio. If EDA, which has four reactive amine hydrogens, reacts at an EDA to EO mole ratio which is greater than 1 4, a mixture of mono-, di-, tri,-, and tetrahydroxyethyl derivatives of EDA are formed. A 10 1 EDA EO feed mole ratio gives predominandy 2-hydroxyethylethylenediamine [111-41-1], the remainder is a mixture of bis-(2-hydroxyethyl)ethylenediamines (7). If the reactive NH to epoxide feed mole ratio is less than one and, additionally, a strong basic catalyst is used, then oxyalkyl derivatives, like those shown for EDA and excess PO result (8,9). 

The most important Lewis bases are tertiary amines or polyamines converted into tertiary amines upon reaction with epoxide groups. 

Mechanisms for reaction of tertiary amines with epoxides are discussed in References 16 and 17. 

RSSR (R = Me, Ph, Bu), BU3P, rt, 15-83% yield." This reagent also reacts with epoxides to form 1,2-dithioethers. 

An important development of polymerisation casting is that of reaction injection moulding. Developed primarily for polyurethanes (and discussed further in Chapter 27), the process has also found some use with polyamides and with epoxide resins. 

The polysulphides used are relatively mobile liquids with viscosities of about 10 poise and are thus useful as reactive diluents. They may be employed in any ratio with epoxide and produets will range from soft rubbers, where only polysulphides are employed, to hard resins using only epoxide. 

NBP reacts with epoxides according to I to yield methine dyestuffs [14] and with alkylating agents (R-X, X = e.g. halogen) according to II to yield colored pigments [15]. 

In some cases products of rearrangement are obtained either partially or exclusively on treatment of Grignard reagents with epoxides. Thus, reaction of the 2/ ,3/ -epoxide (14) with methyl Grignard reagent affords a mixture of two epimeric secondary A-nor alcohols (15) in 80% yield and the tertiary hydroxy compound, 2a-methyl-5a-cholestan-2/f-ol (16) in 15 % yield. ... 

Diethylaminosulfur trifluoride (DAST) reacts with epoxides to give com plex mixtures in which vicinal as difluorides, gemmal difluorides, and bis(2-fluoroalkyl) ethers are the mam components I6 (equations 16 and 17)... 

Difluoronitroethanol m aqueous alkaline solutions reacts readily with methyl bromoacetate [/] and with epoxides [2] (equation 1)... 

Sodium iodide in trifluoroacetic anhydride reacts with epoxides to form the corresponding alkenes in high yields [39] The reduction is stereospecific and generates olefins of the same geometry as the starting epoxides [39]... 

Alkylation of enamines with epoxides or acetoxybromoalkanes provided intermediates for cyclic enol ethers (668) and branched chain sugars were obtained by enamine alkylation (669). Sodium enolates of vinylogous amides underwent carbon and nitrogen methylation (570), while vicinal endiamines formed bis-quaternary amonium salts (647). Reactions of enamines with a cyclopropenyl cation gave alkylated imonium products (57/), and 2-benzylidene-3-methylbenzothiazoline was shown to undergo enamine alkylation and acylation (572). A cyclic enamine was alkylated with methylbromoacetate and the product reduced with sodium borohydride to the key intermediate in a synthesis of the quebrachamine skeleton (57i). 

Grignard reagents do react with epoxides 24 by an SN2-mechanism, resulting in a ring-opening reaction. An epoxide carbon bearing no additional substituent—i.e. a methylene group—is more reactive towards nucleophilic attack than a substituted one ... 

Construction of the A ring fragment starts with epoxidation of chiral d-carvone (114) to afford epoxide 115. 

Epoxide resins are essentially long-chain polyhydric alcohols with epoxide groups at either end. They make useful building blocks because both the hydroxyl and the epoxide groups are available for reaction with other compounds. 

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