Addition: compounds, 119 reactions

Figure 7.3 Concentrations in molkg as a function of time in a semi-batch reactor with the fast addition reaction. Compound B is fed at constant rate within 4 hours in a stoichiometric excess of 25%. B is fed in stoichiometric amounts.

MarkownikofT s rule The rule states that in the addition of hydrogen halides to an ethyl-enic double bond, the halogen attaches itself to the carbon atom united to the smaller number of hydrogen atoms. The rule may generally be relied on to predict the major product of such an addition and may be easily understood by considering the relative stabilities of the alternative carbenium ions produced by protonation of the alkene in some cases some of the alternative compound is formed. The rule usually breaks down for hydrogen bromide addition reactions if traces of peroxides are present (anti-MarkownikofT addition). 

However, the term saturated is often applied to compounds containing double or triple bonds which do not easily undergo addition reactions. Thus ethanoic acid is termed a saturated carboxylic acid and acetonitrile a saturated nitrile, whereas a Schiff base is considered to be unsaturated. 

Compounds are stored in reaction databases as connection tables (CT) in the same manner as in structure databases (see Section 5.11). Additionally, each compound is assigned information on the reaction center and the role of each compound in the specific reaction scheme (educt, product, etc.) (see Chapter 3). In addition to reaction data, the reaction database also includes bibliographic and factual information (solvent, yield, etc.). All these different data types render the integrated databases quite complex. The retrieval software must be able to recall all these different types of information. 

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]. 

In the reaction of 2-aminoselenazoIe with ethyl propiolate, in addition to compound type 7 (50% yield), compounds 8 and 9 were also isolated. Compound 7 is probably formed through the cis isomer of 8 (Scheme 55). 

Conjugate acid (Section 1 13) The species formed from a Brpnsted base after it has accepted a proton Conjugate addition (Sections 1010 and 1812) Addition reaction in which the reagent adds to the termini of the con jugated system with migration of the double bond synony mous with 1 4 addition The most common examples include conjugate addition to 1 3 dienes and to a 3 unsaturated car bonyl compounds... 

Nylon 6, 11, and 12. This class of polymers is polymerized by addition reactions of ring compounds that contain both acid and amine groups on the monomer. 

Michael condensations are catalyzed by alkaU alkoxides, tertiary amines, and quaternary bases and salts. Active methylene compounds and aUphatic nitro compounds add to form P-substituted propionates. These addition reactions are frequendy reversible at high temperatures. Exceptions are the tertiary nitro adducts which are converted to olefins at elevated temperatures (24). 

Methacryhc acid and its ester derivatives are Ctfjy -unsaturated carbonyl compounds and exhibit the reactivity typical of this class of compounds, ie, Michael and Michael-type conjugate addition reactions and a variety of cycloaddition and related reactions. Although less reactive than the corresponding acrylates as the result of the electron-donating effect and the steric hindrance of the a-methyl group, methacrylates readily undergo a wide variety of reactions and are valuable intermediates in many synthetic procedures. 

In the examples, a nitro group is substituted for a hydrogen atom, and water is a by-product. Nitro groups may, however, be substituted for other atoms or groups of atoms. In Victor Meyer reactions which use silver nitrite, the nitro group replaces a hahde atom, eg, I or Br. In a modification of this method, sodium nitrite dissolved in dimethyl formamide or other suitable solvent is used instead of silver nitrite (1). Nitro compounds can also be produced by addition reactions, eg, the reaction of nitric acid or nitrogen dioxide with unsaturated compounds such as olefins or acetylenes. 

C-Allyl Complex Formation. AHyl hahde, aHyl ester, and other aHyl compounds undergo oxidative addition reactions with low atomic valent metal complexes to form TT-aHyl complexes. This is a specific reaction of aHyl compounds. 

Also, Michael addition reactions occur between Ai-acylaminomalonic acid esters and unsaturated compounds, ie, acrolein [107-02-8] acrylonitrile [107-13-1y, acryhc acid esters, and amino acids result from hydrolysis of the addition products. 

Toluene, an aLkylben2ene, has the chemistry typical of each example of this type of compound. However, the typical aromatic ring or alkene reactions are affected by the presence of the other group as a substituent. Except for hydrogenation and oxidation, the most important reactions involve either electrophilic substitution in the aromatic ring or free-radical substitution on the methyl group. Addition reactions to the double bonds of the ring and disproportionation of two toluene molecules to yield one molecule of benzene and one molecule of xylene also occur. 

Vanillin is a compound that possesses both a phenoHc and an aldehydic group. It is capable of undergoing a number of different types of chemical reactions. Addition reactions are possible owing to the reactivity of the aromatic nucleus. 

Condensation of vinyl chloride with formaldehyde and HCl (Prins reaction) yields 3,3-dichloro-l-propanol [83682-72-8] and 2,3-dichloro-l-propanol [616-23-9]. The 1,1-addition of chloroform [67-66-3] as well as the addition of other polyhalogen compounds to vinyl chloride are cataly2ed by transition-metal complexes (58). In the presence of iron pentacarbonyl [13463-40-6] both bromoform [75-25-2] CHBr, and iodoform [75-47-8] CHl, add to vinyl chloride (59,60). Other useful products of vinyl chloride addition reactions include 2,2-di luoro-4-chloro-l,3-dioxolane [162970-83-4] (61), 2-chloro-l-propanol [78-89-7] (62), 2-chloropropionaldehyde [683-50-1] (63), 4-nitrophenyl-p,p-dichloroethyl ketone [31689-13-1] (64), and p,p-dichloroethyl phenyl sulfone [3123-10-2] (65). 

Poly(vinyl alcohol) undergoes Michaels addition with compounds containing activated double bonds, including acrylonitrile (145—150), acrylamide (151—153), A/-methylolacrylamide (154—156), methyl vinyl ketone (157,158), acrolein (157), and sodium 2-acrylamido-2-methylpropanesulfonate (159). The reactions have been carried out under conditions spanning from homogeneous reactions in solvent to heterogeneous reactions occurring in the swollen powder or fiber. 

Methylarsine, trifluoromethylarsine, and bis(trifluoromethyl)arsine [371-74-4] C2HAsF, are gases at room temperature all other primary and secondary arsines are liquids or solids. These compounds are extremely sensitive to oxygen, and ia some cases are spontaneously inflammable ia air (45). They readily undergo addition reactions with alkenes (51), alkynes (52), aldehydes (qv) (53), ketones (qv) (54), isocyanates (55), and a2o compounds (56). They also react with diborane (43) and a variety of other Lewis acids. Alkyl haUdes react with primary and secondary arsiaes to yield quaternary arsenic compounds (57). 

A number of BMI resias based on this chemistry became commercially available through Rhc ne Poulenc for appHcation ia priated circuit boards and mol ding compounds and Rhc ne Poulenc recognized the potential of bismaleimides as building blocks for temperature-resistant thermoset systems. The basic chemistry, however, was not new, because the Michael addition reaction had been employed by Du Pont to obtain elastomeric reaction products from bismaleimides and Hquid polymeric organic diamines (15). 

Etherification. The accessible, available hydroxyl groups on the 2, 3, and 6 positions of the anhydroglucose residue are quite reactive (40) and provide sites for much of the current modification of cotton ceUulose to impart special or value-added properties. The two most common classes into which modifications fall include etherification and esterification of the cotton ceUulose hydroxyls as weU as addition reactions with certain unsaturated compounds to produce ceUulose ethers (see Cellulose, ethers). One large class of ceUulose-reactive dyestuffs in commercial use attaches to the ceUulose through an alkaH-catalyzed etherification by nucleophilic attack of the chlorotriazine moiety of the dyestuff ... 

Cyclopentadiene contains conjugated double bonds and an active methylene group and can thus undergo a Diels-Alder diene addition reaction with almost any unsaturated compound, eg, olefins, acetylene, maleic anhydride, etc. The number of its derivatives is extensive only the reactions and derivatives considered most important are discussed. 

These effects can be attributed mainly to the inductive nature of the chlorine atoms, which reduces the electron density at position 4 and increases polarization of the 3,4-double bond. The dual reactivity of the chloropteridines has been further confirmed by the preparation of new adducts and substitution products. The addition reaction competes successfully, in a preparative sense, with the substitution reaction, if the latter is slowed down by a low temperature and a non-polar solvent. Compounds (12) and (13) react with dry ammonia in benzene at 5 °C to yield the 3,4-adducts (IS), which were shown by IR spectroscopy to contain little or none of the corresponding substitution product. The adducts decompose slowly in air and almost instantaneously in water or ethanol to give the original chloropteridine and ammonia. Certain other amines behave similarly, forming adducts which can be stored for a few days at -20 °C. Treatment of (12) and (13) in acetone with hydrogen sulfide or toluene-a-thiol gives adducts of the same type. 

Potential 2,5-dihydroxy compounds (185) exist in the dicarbonyl forms (186). Succinic anhydride (186 Z = O) on silylation is converted into 2,5-bis(trimethylsilyloxy)furan (187) the latter compound readily participates in Diels-Alder addition reactions (80TL3423). Reaction of thiosuccinic anhydride (186 Z = S) with the triphenylphosphorane Et02CH=PPh3 gives a product which exists in the aromatic form (188) (75LA1967). 

Addition nomenclature, 1, 37 Addition reactions heterocyclic compounds reviews, 1, 70 Additives... 

Azirine, trans-2-methyl-3-phenyl-racemization, 7, 33, 34 1-Azirine, 2-phenyl-reactions, 7, 69 with carbon disulfide, S, 153 1-Azirine, 3-vinyl-rearrangements, 7, 67 Azirines, 7, 47-93 cycloaddition reactions, 7, 26 fused ring derivatives, 7, 47-93 imidazole synthesis from, 5, 487-488 photochemical addition reactions to carbonyl compounds, 7, 56 photolysis, 5, 780, 7, 28 protonated... 

Diazirine, fluoromethoxy-nitrogen extrusion, 7, 224 Diazirine, methylvinyl-rearrangement, 7, 221 Diazirines addition reactions to Grignard compounds, 7, 2 0 as carbene precursors, 7, 236 IR spectra, 7, 203 microwave spectrum, 7, 199 molecular spectra, 7, 202-204 nitrogen extrusion, 7, 223 NMR, 7, 202 photoconversion to diazoalkanes, 7, 234 photoisomerization, 7, 221 photolysis, 7, 225-227 quantum chemical investigations, 7, 197 reactions... 

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