With Olefins

Aryl tellurium trichlorides and tribromides react with terminal and internal linear olefins and with cycloalkenes to produce aryl 2-chloroalkyl tellurium dihalides. The halide ion and the aryldichlorotelluro group approach the olefin from opposite sides of the plane defined by the atoms bonded to the olefinic carbon atoms. These anri -additions yield r reo-addition products from (Z)-olefins, and ery/hro-products from ( )-olefins . 

2-Chloropropyl 2-Naphthyl Tellurium Dichloride A solution of 5.4 g (15 mmol) of 2-naphthyl tellurium trichloride and 1.0 g (24 mmol) of propene in 50 ml of acetonitrile is placed in a 100 m/ tube. The tube is sealed, heated at 70° for 12 h, cooled, and opened. The acetonitrile is evaporated and the residue is recrystallized from acetonitrile yield 4.8 g (79%) m.p. 136-138°. 

Reactions with higher boiling point olefins do not require sealed tubes. Examples of similar reactions are given in Table 17 (p. 546). 

The addition of aryl tellurium trichlorides to trimethylsiloxyethenes is followed by loss of chlorotrimethylsilane and formation of 2-oxo-alkyl aryl tellurium dichlorides - 

Trimethylsilyl ethers of the ends from acetone, tert.-hvAyX methyl ketone, cyclopentanone, cyclohexanone, 2-decalone, phenyl methyl ketone 

---

A fundamental difference exists between conventional acid-catalyzed and superacidic hydrocarbon chemistry. In the former, trivalent car-benium ions are always in equilibrium with olefins, which play the key role, whereas in the latter, hydrocarbon transformation can take place without the involvement of olefins through the intermediacy of five-coordinate carbocations. 

Palladium-catalyzed coupling reactions of organic halides with olefins or dienes (R. F. Heck, 1979) are broad in scope and simple to carry out. Anhydrous conditions or any special technique are not required and most functional groups are tolerated. 

Alkenes in (alkene)dicarbonyl(T -cyclopentadienyl)iron(l+) cations react with carbon nucleophiles to form new C —C bonds (M. Rosenblum, 1974 A.J. Pearson, 1987). Tricarbon-yi(ri -cycIohexadienyI)iron(l-h) cations, prepared from the T] -l,3-cyclohexadiene complexes by hydride abstraction with tritylium cations, react similarly to give 5-substituted 1,3-cyclo-hexadienes, and neutral tricarbonyl(n -l,3-cyciohexadiene)iron complexes can be coupled with olefins by hydrogen transfer at > 140°C. These reactions proceed regio- and stereospecifically in the successive cyanide addition and spirocyclization at an optically pure N-allyl-N-phenyl-1,3-cyclohexadiene-l-carboxamide iron complex (A.J. Pearson, 1989). 

Thallium(III) acetate reacts with alkenes to give 1,2-diol derivatives (see p. 128) while thallium(III) nitrate leads mostly to rearranged carbonyl compounds via organothallium compounds (E.C. Taylor, 1970, 1976 R.J. Ouelette, 1973 W. Rotermund, 1975 R. Criegee, 1979). Very useful reactions in complex syntheses have been those with olefins and ketones (see p. 136) containing conjugated aromatic substituents, e.g. porphyrins (G. W. Kenner, 1973 K.M. Smith, 1975). 

Conjugation with olefinic or acetylenic groups lowers the frequency and raises the intensity. Conjugation with carbonyl groups usually has little effect on the position of absorption. 

Chloroacetate esters are usually made by removing water from a mixture of chloroacetic acid and the corresponding alcohol. Reaction of alcohol with chloroacetyl chloride is an anhydrous process which Hberates HCl. Chloroacetic acid will react with olefins in the presence of a catalyst to yield chloroacetate esters. Dichloroacetic and trichloroacetic acid esters are also known. These esters are usehil in synthesis. They are more reactive than the parent acids. Ethyl chloroacetate can be converted to sodium fluoroacetate by reaction with potassium fluoride (see Fluorine compounds, organic). Both methyl and ethyl chloroacetate are used as agricultural and pharmaceutical intermediates, specialty solvents, flavors, and fragrances. Methyl chloroacetate and P ionone undergo a Dar2ens reaction to form an intermediate in the synthesis of Vitamin A. Reaction of methyl chloroacetate with ammonia produces chloroacetamide [79-07-2] C2H ClNO (53). 

The use of silver fluoroborate as a catalyst or reagent often depends on the precipitation of a silver haUde. Thus the silver ion abstracts a CU from a rhodium chloride complex, ((CgH )2As)2(CO)RhCl, yielding the cationic rhodium fluoroborate [30935-54-7] hydrogenation catalyst (99). The complexing tendency of olefins for AgBF has led to the development of chemisorption methods for ethylene separation (100,101). Copper(I) fluoroborate [14708-11-3] also forms complexes with olefins hydrocarbon separations are effected by similar means (102). 

An important synthetic process for forming a new carbon—carbon bond is the acid-catalyzed condensation of formaldehyde with olefins (Prins reaction) ... 

In acetic acid solvent, ethylene gives 1,3-propanediol acetates (46) and propylene gives 1,3-butanediol acetates (47). A similar reaction readily occurs with olefinic alcohols and ethers, diolefins, and mercaptans (48). 

The formyl cation, HCO, is also likely to be an intermediate in the modification of the Koch reaction whereby formic acid reacts with olefins to give carboxyhc acids (20) ... 

This reaction occurs readily ia the presence of sulfuric or hydrofluoric acid. In the absence of such strong acids, formic acid reacts readily with olefins to give formate esters (21). 

Sulfonated styrene—divinylbensene cross-linked polymers have been appHed in many of the previously mentioned reactions and also in the acylation of thiophene with acetic anhydride and acetyl chloride (209). Resins of this type (Dowex 50, Amherljte IR-112, and Permutit Q) are particularly effective catalysts in the alkylation of phenols with olefins (such as propylene, isobutylene, diisobutylene), alkyl haUdes, and alcohols (210) (see Ion exchange). Superacids. 

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). 

Its reactions with olefins, governed by steric rather than electronic factors, are very sluggish. Even simple 1-alkenes require 8 h at 25°C for complete reaction. In contrast, alkynes are hydroborated with great ease to alkenylboranes, high steric requirements of the reagent preventing dihydroboration (117). 

Hydrogen atoms ate thought to play a principal role in the mechanistic steps of many reactions, including hydrocarbon thermolysis (119). Some reactions of atomic hydrogen with olefins and paraffins ate the following (120—122) ... 

Chlorine can be removed by either activated carbon adsorption or by reaction with olefins such as ethylene over-activated carbon at temperatures of 30—200°C (44). Addition of Hquid high boiling paraffins can reduce the chlorine content in the HCl gas to less than 0.01% (45). 

Blends ofiPetramethylbisphenolA-PC (TMBPA-PC) with ModfiedPS or Styrene-Ac7ylonitrile(SAN) Copolymer. By installing halogen atoms on the aromatic rings of the PC-backbone, not only the resistance to heat softening can be increased (eg, TMBPA-PC = 203° C) (209), but also the compatibiUty with olefins. 

Chlorine heptoxide is more stable than either chlorine monoxide or chlorine dioxide however, the CX C) detonates when heated or subjected to shock. It melts at —91.5°C, bods at 80°C, has a molecular weight of 182.914, a heat of vapori2ation of 34.7 kj/mol (8.29 kcal/mol), and, at 0°C, a vapor pressure of 3.2 kPa (23.7 mm Hg) and a density of 1.86 g/mL (14,15). The infrared spectmm is consistent with the stmcture O CIOCIO (16). Cl O decomposes to chlorine and oxygen at low (0.2—10.7 kPa (1.5—80 mm Hg)) pressures and in a temperature range of 100—120°C (17). It is soluble in ben2ene, slowly attacking the solvent with water to form perchloric acid it also reacts with iodine to form iodine pentoxide and explodes on contact with a flame or by percussion. Reaction with olefins yields the impact-sensitive alkyl perchlorates (18). 

Singlet oxygen reacts with olefins presumably by the "ene" reaction to form allyflc hydroperoxides (45,57), eg, l-methyl-2-propenyl hydroperoxide [20733-08-8] is produced from 2-butene (eq. 19). The regioselectivity of this reaction has been investigated (58). 

Phosphorus(V) sulfide reacts with olefins, amines, Grignard reagents, and terpenes (6,26) as follows ... 

In the presence of a large excess of PH, primary phosphines, RPH2, are formed predominantiy. Secondary phosphines, R2PH, must be either isolated from mixtures with primary and tertiary products or made in special multistep procedures. Certain secondary phosphines can be produced if steric factors preclude conversion to a tertiary product. Both primary and secondary phosphines can be substituted with olefins. After the proper selection of substituents, mixed phosphines of the type RRTH or RR R T can be made. 

Polynuclear Aromatics. The alkylation of polynuclear aromatics with olefins and olefin-producing reagents is effected by acid catalysts. The alkylated products are more compHcated than are those produced by the alkylation of benzene because polynuclear aromatics have more than one position for substitution. For instance, the alkylation of naphthalene [91-20-3] with methanol over mordenite and Y-type zeoHtes at 400—450°C produces 1-methylnaphthalene [90-12-0] and 2-methylnaphthalene at a 2-/1- ratio of about 1.8. The selectivity to 2-methylnaphthalene [91-57-6] is increased by applying a ZSM-5 catalyst to give a 2-/1- ratio of about 8 (102). 

All lation of Aromatic Amines and Pyridines. Commercially important aromatic amines are aniline [62-53-3] toluidine [26915-12-8], phenylenediamines [25265-76-3], and toluenediamines [25376-45-8] (see Amines, aromatic). The ortho alkylation of these aromatic amines with olefins, alcohols, and dienes to produce more valuable derivatives can be achieved with soHd acid catalysts. For instance, 5-/ f2 butyl-2,4-toluenediamine (C H gN2), which is used for performance polymer appHcations, is produced at 85% selectivity and 84% 2,4-toluenediamine [95-80-7] (2,4-4L)A)... 

G-All lation. Siace para-alkylated derivatives of DPA are widely used ia large volumes as antioxidants (qv), the most important reaction of DPA is the acid catalyzed reaction with olefins (2,3). Alkylation is carried out by adding the olefin to a mixture of DPA and an acid catalyst, such as AIQ. ... 

Etherification. Ethers of amyl alcohols have been prepared by reaction with ben2hydrol (63), activated aromatic haUdes (64), dehydration-addition reactions (65), addition to olefins (66—71), alkoxylation with olefin oxides (72,73) and displacement reactions involving thek alkah metal salts (74—76). 

Olefin Complexes. Silver ion forms complexes with olefins and many aromatic compounds. As a general rule, the stabihty of olefin complexes decreases as alkyl groups are substituted for the hydrogen bonded to the ethylene carbon atoms (19). 

Hydrogen sulfide reacts with olefins under various conditions forming mercaptans and sulfides (108,109). With ethylene it can react to ultimately give diethyl sulfide (110). With unsymmetrical olefins, the direction of addition can be controlled by the choice of either a free-radical initiator, including ultraviolet light, or an acidic catalyst (110) ... 

Numerous organic reactions of sulfur monochloride are of practical and commercial importance. Of particular importance is the reaction of sulfur monochloride with olefins to yield various types of addition products (142). With ethylene, the severe vesicant bis(2-chloroethyl) sulfide [505-60-2] (mustard gas) forms with elemental sulfur and polysulfides (see Chemicals IN war). Propylene reacts similarly ... 

---