2- Butene preparation

Although dimeric (t-butylmethyleneamino)dibutylborane can be prepared by the reaction of tri-t-butylborane with pivalonitrile at temperature above 150 °C by elimination of butene. preparation at lower temperatures involving triethylamine-borane according to Eq. (11), illustrates that the formation of this iminoborane proceeds via di-n-butylborane as an intermediate 6 ... 

Preparation of 3,5-dimethyl-4-(trifluoromethyl)-2,5-heptadien-4-ol. A 1-L, three-necked, round-bottomed flask, equipped with a reflux condenser, a magnetic stir bar and an addition funnel is flame dried under an atmosphere of argon. After the apparatus has cooled, 350 mL of anhydrous diethyl ether (freshly distilled from sodium benzophenone10 under argon) is added. Lithium wire (6.9 g, 1.0 mol, 3.2-mm diameter, 0.01% Na content, Aldrich Chem. Co., Milwaukee, WI), which is cut into 5- to 10-mm pieces and washed with hexanes, is added to the flask under a counterstream of argon gas. The reaction flask is cooled to 0°C in an ice bath and 68.9 g (0.51 mol) of 2-bromo-cis-2-butene (prepared in the previous step9) in 50 mL of anhydrous diethyl ether is added dropwise over a 45-min period while the reaction mixture is stirred. The reaction solution becomes cloudy due to the formation of lithium bromide. Stirring is continued for an additional 1.5-2 h at 0°C. 

Secondary butyl alcohol, methylethyl car-binol, 2-butanol, CH3CH2CH(Me)OH. B.p. I00°C. Manufactured from the butane-butene fraction of the gas from the cracking of petroleum. Used to prepare butanone. 

Butene, a-bulylene, CH3CH2CH CH2-Prepared by passing the vapour of 1-butanol over heated alumina. 

For general reactions see olefins. The butylenes are used to prepare 2-butanol. I-Butene and isobutene are formed into widely used polymers. 

HOCH2CH2CH2CH2OH. B.p. 228"C. Prepared ethyne plus methanal, hydrogenated to butanediol. Used in production of y-buty-rolactone and 2-pyrrolidone. Widely used in polyurethane products, butylenes See butenes. 

Zinc acetylides, prepared in situ by the treatment of lithium acetylides with ZnCF, are widely used. The zinc acetylide 311, prepared in situ, reacts with (Z)-3-iodo-2-buten-l-ol (312) with nearly complete retention of stereochemistry to afford an important intermediate 313 for carotenoid synthesis[227]. 

Diacetates of 1,4-butenediol derivatives are useful for double allylation to give cyclic compounds. l,4-Diacetoxy-2-butene (126) reacts with the cyclohexanone enamine 125 to give bicyclo[4.3.1]decenone (127) and vinylbicy-clo[3.2.1]octanone (128)[85,86]. The reaction of the 3-ketoglutarate 130 with cij-cyclopentene-3,5-diacetate (129) affords the furan derivative 131 [87]. The C- and 0-allylations of ambident lithium [(phenylsulfonyl)methylene]nitronate (132) with 129 give isoxazoline-2-oxide 133, which is converted into c -3-hydroxy-4-cyanocyclopentene (134)[S8]. Similarly, chiral m-3-amino-4-hyd-roxycyclopentene was prepared by the cyclization of yV-tosylcarbamate[89]. 

Hydrometallation is catalyzed by Pd. Hydroboration of l-buten-2-methyl-3-yne (197) with catecholborane (198) gives the 1,4-adduct 199 with 84% selectivity. The ratio of Pd to phosphine (1 1.5) is important[l 10]. The vinyl sulfide 201 is prepared by a one-pot reaction of the thioalkyne 200 via a Pd-catalyzed hydroborution-coupling sequence using dppf as a ligand[l 11]. 

Since the exocyclic sulfur is more reactive in the ambident anion than in A-4-thiazoIine-2-thione. greater nucleophilic reactivity is to be expected. Thus a large variety of thioethers were prepared in good yields starting from alkylhalides (e.g.. Scheme 38 (54, 91, 111, 166-179). lactones (54, 160), aryl halides (54, 152. 180, 181), acyl chlorides (54. 149, 182-184). halothiazoles (54, 185-190), a-haloesters (149. 152. 177. 191-194), cyanuric chloride (151). fV.N-dimethylthiocarbamoyl chloride (151, 152. 195. 196), /3-chloroethyl ester of acrylic acid (197), (3-dimethylaminoethyl chloride (152). l,4-dichloro-2-butyne (152), 1,4-dichloro-2-butene (152), and 2-chloro-propionitrile (152). A general... 

As a method for the preparation of alkenes a weakness in the acid catalyzed dehydration of alcohols IS that the initially formed alkene (or mixture of alkenes) sometimes isomenzes under the conditions of its formation Write a stepwise mechanism showing how 2 methyl 1 butene might isomenze to 2 methyl 2 butene in the presence of sulfuric acid... 

Monosubstituted Boranes. Only a few monoaLkylboranes are directiy available by hydroboration. Tertiary hexylborane, 2,3-dimethyl-2-butylborane [3688-24-2] (thexylborane, Thx) BH2 (5), easily prepared from 2,3-dimethyl-2-butene, is the best studied (3,60—62). It should be... 

Acetylene is condensed with carbonyl compounds to give a wide variety of products, some of which are the substrates for the preparation of families of derivatives. The most commercially significant reaction is the condensation of acetylene with formaldehyde. The reaction does not proceed well with base catalysis which works well with other carbonyl compounds and it was discovered by Reppe (33) that acetylene under pressure (304 kPa (3 atm), or above) reacts smoothly with formaldehyde at 100°C in the presence of a copper acetyUde complex catalyst. The reaction can be controlled to give either propargyl alcohol or butynediol (see Acetylene-DERIVED chemicals). 2-Butyne-l,4-diol, its hydroxyethyl ethers, and propargyl alcohol are used as corrosion inhibitors. 2,3-Dibromo-2-butene-l,4-diol is used as a flame retardant in polyurethane and other polymer systems (see Bromine compounds Elame retardants). 

Much more important is the hydrogenation product of butynediol, 1,4-butanediol [110-63-4]. The intermediate 2-butene-l,4-diol is also commercially available but has found few uses. 1,4-Butanediol, however, is used widely in polyurethanes and is of increasing interest for the preparation of thermoplastic polyesters, especially the terephthalate. Butanediol is also used as the starting material for a further series of chemicals including tetrahydrofuran, y-butyrolactone, 2-pyrrohdinone, A/-methylpyrrohdinone, and A/-vinylpyrrohdinone (see Acetylene-DERIVED chemicals). The 1,4-butanediol market essentially represents the only growing demand for acetylene as a feedstock. This demand is reported (34) as growing from 54,000 metric tons of acetylene in 1989 to a projected level of 88,000 metric tons in 1994. 

Methyl Isopropyl Ketone. Methyl isopropyl ketone [563-80-4] (3-methyl-2-butanone) is a colorless Hquid with a characteristic odor of lower ketones. It can be produced by hydrating isoprene over an acidic catalyst at 200—300°C (150,151) or by acid-catalyzed condensation of methyl ethyl ketone and formaldehyde to 2-methyl-l-buten-3-one, foUowed by hydrogenation to the product (152). Other patented preparations are known (155,156). Methyl isopropyl ketone is used as an intermediate in the production of pharmaceuticals and fragrances (see Perfumes), and as a solvent (157). It is domestically available from Eastman (Longview, Texas) (47). 

The synthesis of isotactic polymers of higher a-olefins was discovered in 1955, simultaneously with the synthesis of isotactic PP (1,2) syndiotactic polymers of higher a-olefins were first prepared in 1990 (3,4). The first commercial production of isotactic poly(l-butene) [9003-29-6] (PB) and poly(4-methyl-l-pentene) [9016-80-2] (PMP) started in 1965 (5). 

Esters of / fZ-amyl alcohol can be obtained by acylation of 2-methyl-2-butene in the presence of trifluoromethanesulfonic acid (44). The esters produced, in high yields, from reaction of amyl alcohols with carboxyHc anhydrides, are used as intermediates for preparation of pyryflum salts (45,46) and alkaloids (47). Tria2oles prepared by acylation of 3-methyl-1-butanol are useful as herbicides (48). 

In situ preparation of polymer blends of 1,4-polybutadiene with polystyrene, or poly(l-butene) has been achieved by using the heterogeneous Ziegler-Natta type catalyst (C2H )2A1C1—Ti(OC4H )4 in the host polymers (217). Homogeneous catalysts can also be used to catalyze these reactions (218). 

Dicbloro-l,3-butadiene [1653-19-6] is a favored comonomer to decrease the regularity and crystallization of chloroprene polymers. It is one of the few monomers that will copolymerize with chloroprene at a satisfactory rate without severe inhibition. It is prepared from by-products or related intermediates. It is also prepared in several steps from chloroprene beginning with hydrochlorination. Subsequent chlorination to 2,3,4-trichloto-1-butene, followed by dehydrochlorination leads to the desired monomer in good yield if polymerization is prevented. 

It is preferable to prepare tbe 1,2,3,4-tettacblotobutane [3405-32-1] from /n r-l,4-dicbloto-2-butene [110-57-6] wbicb gives mainly tbe meso tetracbloride [28507-96-2] wbicb in turn gives a better yield and bigber isomeric purity of tbe resulting monomer (13). 

Caution Like alt vinyl monomeva, 3-buten-2-one is toxin and the preparation should he aarried out in a ivell-ventilated hood. 

The photolysis of a-diazosulfones dissolved in alkenes provides sulfonyl-substituted cyclopropanes in high yields. This is exemplified by the preparation of l-(p-methoxyphenylsulfonyl)-2,2,3,3-tetra-methylcyclopropane in 75% yield from -methoxybenzenesulfonyl-diazomethane and 2,3-dimethyl-2-butene. A similar addition to [Pg.101]

RAFF, R. A. V. and DOAK, K. w. (Eds.), Crystalline Olefin Polymers, Interscience, New York (1964) RUBIN, I. D., Poly-1-butene its Preparation and Properties, Macdonald, London (1969)... 

Diphenylbutadiene has been obtained from phenylacetic acid and cinnamaldehyde with lead oxide, by the dehydrogenation of l,4-diphenyl-2-butene with butyllithium, and by the coupling reaction of benzenediazonium chloride and cinnamyl-ideneacetic acid." The present method gives better yields than those previously reported, is adaptable to the preparation of a variety of substituted bistyryls, and is relatively easy to carry out. 

The regiochemistry is determined by the regiochemistry of the fluoride ion addition reaction, that is, via the most stable perfluorocarbanion intermediate Von Werner used a similar reaction to prepare silver compounds from perfluoro-2-methyl-2-butene and perfluoro 2 methyl-2-pentene [271] Silver(I) fluoride adds to bis(ttitluoromethyl)ketene in DMF without fluoride ion catalysis [270] The analogous trifluorovinylsulfurpentafluoride reacts similarly to give the isolable pentafluorosulfur derivative [272] (equation 187)... 

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