Dimers amine

Like butadiene, allene undergoes dimerization and addition of nucleophiles to give 1-substituted 3-methyl-2-methylene-3-butenyl compounds. Dimerization-hydration of allene is catalyzed by Pd(0) in the presence of CO2 to give 3-methyl-2-methylene-3-buten-l-ol (1). An addition reaction with. MleOH proceeds without CO2 to give 2-methyl-4-methoxy-3-inethylene-1-butene (2)[1]. Similarly, piperidine reacts with allene to give the dimeric amine 3, and the reaction of malonate affords 4 in good yields. Pd(0) coordinated by maleic anhydride (MA) IS used as a catalyst[2]. 

Figure 42 Structures of the dimeric amine-gallane adduct 510 and the aminogallane 511.

Intermolecular a-dimer cations are known for thioethers but dimeric amine cation species are not well characterized in solution. However, an example was detected in a zeohte the confinement in the narrow channels and the restricted diffusion favor interaction between the two entities. 

Treating 5.5 g of 2-amino-4,5-dimethylthiazole HCl with 0.66 g of solid sodium hydroxide 15 min at 220°C yields 53% of 4.4. 5.5 -tetramethyT 2,2 -dithiazolylamine, whose structure w as proved by identification with the produa obtained from the reaction between dithiobiuret and 3-bromo-2-butanone (467). This result is comparable to the reaction between 2-aminopyridine and its hydrochloride to yield bis(pyridyl-2)amine (468). Gronowitz applied this reaction to 2-aminothiazole, refluxing it with its hydrochloride 4 hr in benzene and obtained the dimeric 2-aminothiazole (236). He proposed a mechanism (Scheme 143) that involves the addition of a proton to the 5-position of the ring to give 234. The carbocation formed then reacts on the 5-position of a second... 

Fig. 8. Rephcation. The amino adenosine X and the pentafluorophenyl ester Y form a hydrogen-bonded dimer XY, prior to reaction between the amine and the activated ester groups (shown in the circle). The reaction product is a <7 -amide conformer cis-Z that isomeri2es to the more stable trans- acnide Z. The rephcative process is cataly2ed by the reaction product Z (also referred to as the template). First, a termolecular complex XYZ is formed from X, Y, and Z.

The two-part epoxy adhesive, readily available in hardware stores or other consumer outlets, comes in two tubes. One tube contains the epoxy resin, the other contains an amine hardener. Common diamine room temperature epoxy curing agents are materials such as the polyamides, available under the trade name Versamid. These polyamides are the reaction products of dimer acids and aUphatic diamines such as diethylenetriamine [111-40-0] ... 

Diborane [19287-45-7] the first hydroborating agent studied, reacts sluggishly with olefins in the gas phase (14,15). In the presence of weak Lewis bases, eg, ethers and sulfides, it undergoes rapid reaction at room temperature or even below 0°C (16—18). The catalytic effect of these compounds on the hydroboration reaction is attributed to the formation of monomeric borane complexes from the borane dimer, eg, borane-tetrahydrofuran [14044-65-6] (1) or borane—dimethyl sulfide [13292-87-0] (2) (19—21). Stronger complexes formed by amines react with olefins at elevated temperatures (22—24). 

Retardation of the reaction rate by the addition of dimethyl sulfide is in accord with this mechanism. Borane—amine complexes and the dibromoborane—dimethyl sulfide complex react similarly (43). Dimeric diaLkylboranes initially dissociate (at rate to the monomers subsequentiy reacting with an olefin at rate (44). For highly reactive olefins > k - (recombination) and the reaction is first-order in the dimer. For slowly reacting olefins k - > and the reaction shows 0.5 order in the dimer. 

Commercially, polymeric MDI is trimerized duting the manufacture of rigid foam to provide improved thermal stabiUty and flammabiUty performance. Numerous catalysts are known to promote the reaction. Tertiary amines and alkaU salts of carboxyUc acids are among the most effective. The common step ia all catalyzed trimerizations is the activatioa of the C=N double boad of the isocyanate group. The example (18) highlights the alkoxide assisted formation of the cycHc dimer and the importance of the subsequent iatermediates. Similar oligomerization steps have beea described previously for other catalysts (61). 

Bond dissociation energies (BDEs) for the oxygen—oxygen and oxygen— hydrogen bonds are 167—184 kj/mol (40.0—44.0 kcal/mol) and 375 kj/mol (89.6 kcal/mol), respectively (10,45). Heats of formation, entropies, andheat capacities of hydroperoxides have been summarized (9). Hydroperoxides exist as hydrogen-bonded dimers in nonpolar solvents and readily form hydrogen-bonded associations with ethers, alcohols, amines, ketones, sulfoxides, and carboxyhc acids (46). Other physical properties of hydroperoxides have been reported (46). 

Addition compounds form with those organics that contain a donor atom, eg, ketonic oxygen, nitrogen, and sulfur. Thus, adducts form with amides, amines, and A/-heterocycles, as well as acid chlorides and ethers. Addition compounds also form with a number of inorganic compounds, eg, POCl (6,120). In many cases, the addition compounds are dimeric, eg, with ethyl acetate, in titanium tetrachloride-rich systems. By using ammonia, a series of amidodichlorides, Ti(NH2) Cl4, is formed (133). 

The octylphenol condensate is used as an additive to lubricating oils and surface-active agents. Other uses of dimer are amination to octylamine and octyldiphenylamine, used in mbber processing hydroformylation to nonyl alcohol for phthalate production and carboxylation via Koch synthesis to yield acids in formulating paint driers (see Drying). 

The properties of 1,1-dichloroethane are Hsted ia Table 1. 1,1-Dichloroethane decomposes at 356—453°C by a homogeneous first-order dehydrochlofination, giving vinyl chloride and hydrogen chloride (1,2). Dehydrochlofination can also occur on activated alumina (3,4), magnesium sulfate, or potassium carbonate (5). Dehydrochlofination ia the presence of anhydrous aluminum chloride (6) proceeds readily. The 48-h accelerated oxidation test with 1,1-dichloroethane at reflux temperatures gives a 0.025% yield of hydrogen chloride as compared to 0.4% HCl for trichloroethylene and 0.6% HCl for tetrachloroethylene. Reaction with an amine gives low yields of chloride ion and the dimer 2,3-dichlorobutane, CH CHCICHCICH. 2-Methyl-l,3-dioxaindan [14046-39-0] can be prepared by a reaction of catechol [120-80-9] with 1,1-dichloroethane (7). 

Uninhibited chloroprene suitable for polymerisation must be stored at low temperature (<10° C) under nitrogen if quaUty is to be maintained. Otherwise, dimers or oxidation products are formed and polymerisation activity is unpredictable. Insoluble, autocatalytic "popcorn" polymer can also be formed at ambient or higher temperature without adequate inhibition. For longer term storage, inhibition is required. Phenothiasine [92-84-2] / fZ-butylcatechol [2743-78-17, picric acid [88-89-17, and the ammonium salt of /V-nitroso-/V-pheny1hydroxy1 amine [135-20-6] have been recommended. 

Additions. The addition reactions of ammonia and amines to the cyanamide nitrile group have been thoroughly studied (15). For optimum conditions, the reaction should be carried out ia an aqueous medium at about 140°C. Gradual addition of the cyanamide to the amine salt minimises dimerization. 

Reactive Polyamide Resins. Another significant commercial appHcation of dimer acids is in reactive polyamide resins. These are formed by the reaction of dimer acids with polyamines such as diethylenetriamine to form polyamides containing reactive secondary amine groups (see DiAMlNES AND HIGHER AMINES, aliphatic). In contrast to nonreactive polyamides, these materials are generally Hquids at 25°C. 

Other dimer acid markets include intermediates for nitriles, amines and diisocyanates. Dimers are also used in polyurethanes, in corrosion inhibition uses other than for downweU equipment, as a "mildness" additive for metal-working lubricants, and in fiber glass manufacture. 

Other types of dimer are formed from pteridin-6-one by the action of ammonia and hydrogen sulfide, giving rise to the corresponding dipteridinyl amine (55JCS2690) and sulfide (65JCS27) respectively. Two pteridine nuclei may be connected directly on base treatment... 

Acid chlorides are useful reagents, but when the pyrazole is N- unsubstituted a dimerization occurs and the diketopiperazine (254) is isolated (Section 4.04.2.3.3(x)). However, (254) reacts with many compounds as an acid chloride would, for example with amines to yield amides (67HC(22)l). The difunctional pyrazole derivative (441) affords polymers by reaction with diphenols (69RRC763). Cyanopyrazoles can be hydrolyzed to the corresponding carboxylic acids (68CB829). 

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