Isobutylene carboxylation

The reaction of trivalent carbocations with carbon monoxide giving acyl cations is the key step in the well-known and industrially used Koch-Haaf reaction of preparing branched carboxylic acids from al-kenes or alcohols. For example, in this way, isobutylene or tert-hutyi alcohol is converted into pivalic acid. In contrast, based on the superacidic activation of electrophiles leading the superelectrophiles (see Chapter 12), we found it possible to formylate isoalkanes to aldehydes, which subsequently rearrange to their corresponding branched ketones. 

Highly Branched Acids. These acids, called neoacids, are produced from highly branched olefins, carbon monoxide, and an acid catalyst such as sulfuric acid, hydrogen fluoride, or boron trifluoride. 2,2,2-Trimethylacetic acid (pivaUc acid) is made from isobutylene and neodecanoic acid is produced from propylene trimer (see Carboxylic Acids, trialkylacetic acids). 

Rhodium catalyst is used to convert linear alpha-olefins to heptanoic and pelargonic acids (see Carboxylic acids, manufacture). These acids can also be made from the ozonolysis of oleic acid, as done by the Henkel Corp. Emery Group, or by steam cracking methyl ricinoleate, a by-product of the manufacture of nylon-11, an Atochem process in France (4). Neoacids are derived from isobutylene and nonene (4) (see Carboxylic acids, trialkylacetic acids). 

Isobutylene, cat. coned. H2SO4, CH Cl, 25°, 6-10 h, 93% yield. These conditions also convert carboxylic acids to /-butyl esters. 

According to the above reaction scheme the carbonylation reaction has to be carried out in two steps In the absence of water the olefin is first converted at 20-80°C and 20-100 bar by the aid of mineralic acid and carbon monoxide into an acyliumion. In a second step the acyliumion reacts with water to the carboxylic acid. The mineral acid catalyst is recovered and can be recycled. The formation of tertiary carboxylic acids (carboxylic acids of the pivalic acid type) is enhanced by rising temperature and decreasing CO pressure in the first step of the reaction. Only tertiary carboxylic acids are formed from olefins that have at the same C atom a branching and a double bond (isobutylene-type olefins). 

Complementary to the work with aqueous acidic media is the study of the homolytic decompositions of Co(III) carboxylates in carboxylic acid media by Lande and Kochi . For example, Co(III) is reduced in pivalic acid media with first-order kinetics with E = 30.6 kcal.mole , AS = 8 eu and k ko = 1.28+0.10 (69 °C). The main oxidation products were found to be isobutylene and tert-butyl pivalate, which suggests that (CH3)3C- is an intermediate. Oxidative decarboxylation is the probable course in the analogous oxidations of n-butyric and isobutyric acids, in view of the production of propane and CO2 under normal... 

Subsequently, Lowenthal and co-workers,3 la,9 Evans et al.,31b and Muller et al.98 reported chiral bis(oxazoline) ligands 185, 186, and 83 as shown in Figure 5-12. The gem-dimethyl [(bis)oxazoline] 83-coordinated copper catalyst is the most widely used ligand. The catalyst is prepared in situ by mixing ligand 83 with an equal molar amount of CuOTf. Asymmetric cyclopropanation of isobutylene with ethyl diazoacetate (EDA) gives ethyl 2,3-dimethylcyclopro-pane carboxylate with >99% ee. 

Solutions of nitric acid in chlorinated solvents can add to some alkenes to give nitrate esters. Some tertiary nitrate esters can be prepared in this way isobutylene (49) reacts with fuming nitric acid of 98.6 % concentration in methylene chloride to give ferf-butyl nitrate (50). However, the products obtained depend on both the substrate and the reaction conditions /3-nitro-nitrate esters, vic-dinitrate esters, /3-nitroalcohols and nitroalkenes have been reported as products with other alkenes. Oxidation products like carboxylic acids are also common, especially at elevated temperatures and in the presence of oxygen. The reaction of alkenes with fuming nitric acid is an important route to unsaturated nitrosteroids, which assumedly arise from the dehydration of /3-nitroalcohols or the elimination of nitric acid from /3-nitro-nitrate... 

Several polymers based on 1,3-dienes are used as elastomers. These include styrene-1,3-butadiene (SBR), styrene-1,3-butadiene terpolymer with an unsaturated carboxylic acid (carboxylated SBR), acrylonitrile-1,3-butadiene (NBR or nitrile rubber) (Secs. 6-8a, 6-8e), isobutylene-isoprene (butyl rubber) (Sec. 5-2i-l), and block copolymers of isoprene or... 

By in situ MAS NMR spectroscopy, the Koch reaction was also observed upon co-adsorption of butyl alcohols (tert-butyl, isobutyl, and -butyl) and carbon monoxide or of olefins (Ao-butylene and 1-octene), carbon monoxide, and water on HZSM-5 (Ksi/ Ai — 49) under mild conditions (87,88). Under the same conditions, but in the absence of water (89), it was shown that ethylene, isobutylene, and 1-octene undergo the Friedel-Crafts acylation (90) to form unsaturated ketones and stable cyclic five-membered ring carboxonium ions instead of carboxylic acids. Carbonylation of benzene by the direct reaction of benzene and carbon monoxide on solid catalysts was reported by Clingenpeel et al. (91,92). By C MAS NMR spectroscopy, the formation of benzoic acid (178 ppm) and benzaldehyde (206 ppm) was observed on zeolite HY (91), AlC -doped HY (91), and sulfated zirconia (SZA) (92). 

The reaction is also called hydrocarboxylation. According to a later modification, the alkene first reacts with carbon monoxide in the presence of the acid to form an acyl cation, which then is hydrolyzed with water to give the carboxylic acid.97 The advantage of this two-step synthesis is that it requires only medium pressure (100 atm). Aqueous HF (85-95%) gave good results in the carboxylation of alkenes and cycloalkenes.98 Phosphoric acid is also effective in the carboxylation of terminal alkenes and isobutylene, but it causes substantial oligomerization as well.99 100 Neocarboxylic acids are manufactured industrially with this process (see Section 7.2.4). The addition may also be performed with formic acid as the source of CO (Koch-Haaf reaction).101 102 The mechanism involves carbocation formation via protonation of the alkene97 103 [Eq. (7.10)]. It then reacts with carbon monoxide... 

Neocarboxylic Acids. The acid-catalyzed carboxylation of alkenes with carbon monoxide in the presence of water is used commercially to produce neocarboxylic acids.82 Pivalic acid from isobutylene is the most important product. A number of... 

Formation of carboxylic acids from ethylene, isobutylene, and 1-octene was observed by in situ 13C solid-state MAS NMR over H-ZSM-5 zeolite at 23-100°C.298 A systematic study with various Pd complexes revealed that styrene is transformed into 2-phenylpropionic acid as the major product when monophosphine ligands were applied, whereas 3-phenylpropionic acid was obtained in the presence of diphosphines 299... 

Figure 3 describes the preparation of A-co-undecenoyl-L-valine CSP bonded to silica gel. The carboxylic acid group of L-valine was protected by the reaction with isobutylene using the method of Roeske [47]. The formed tert-butyl ester of L-valine was precipitated from diethyl ether as the oxalate by the dropwise addition of a solution of 10% oxalic acid in absolute ethanol. The precipitate is dried and the oxalate group is removed by the reaction of sodium hydroxide. The tert-butyl ester of L-valine was treated with undecenoic acid in tetrahydrofuran (THF), which resulted in A-co-undecenoyl-L-valine methyl ester. In another step, lOmM of monochlorosilane was dissolved in 20 mL of dry pyridine and was allowed to react with /V -to - u ndccenoyl-L-valine methyl ester. 

The /-butyl ester is often prepared by acid-catalyzed addition of the carboxylic acid to isobutylene. The overall protection-deprotection sequence is outlined in the following equation. Note that the /-butyl group is removed in the last step without destroying the phosphorus ester or the amide or benzyl ester groups. 

For the manufacture of non-crosslinked ionomer polymer mixtures ethylene, butene-1, isobutylene, vinyl chloride, vinylidene chloride, aliphatic carboxylic acids of vinyl esters (C2-C18), aliphatic unsaturated mono and di carboxylic organic acid esters (C3-C8) with mono aliphatic saturated alcohols (C2-C12) and unsaturated aliphatic mono and di carboxylic organic acids (C3-C8) can be used as raw materials. 

Ester ation. Carboxylic acids react with alkyl t-butyl ethers in the presence of catalytic amounts of sulfuric acid or />-(oluenesulfonic acid to form esters. Yields are generally good to excellent. The reaction is carried out by heating the reactants cither under reflux or on a steam hath for several minutes until the evolution of isobutylene ceases. 

Lewis acids are seldom effective sdone rather they require the presence of trace amounts of water or some other proton donor (protogen) such as hydrogen halide, alcohol, and carboxylic acid, or a carbocation donor (cationogen) such as t-butyl chloride or triphenylmethyl chloride, which, on reaction with the Lewis acid, forms the electrophilic species that initiates polymerization. Thus dry isobutylene is unaffected by dry boron trifluoride but polymerization occurs immediately when trace amounts of water are added. The initiation process for boron trifluoride and water is... 

A specialty class of carboxyl containing elastomers are the telechelic ionomers. In these systems the carboxyl functionality terminates both ends of the polymer chain. Such polymers range in molecular weight from 1500 to about 6000. These materials can be prepared via several synthetic routes involving anionic or free radical initiated polymeri-zation(32-34). Recently, telechelic sulfonate ionomers of poly-isobutylene have been synthesized(35). These systems offer an unusual opportunity to assess the influence of chain length, chain architecture, cation type, and the Influence of polar additives on ionomer properties. 

Tyr derivatives are prepared after protection of the amino and carboxyl groups either as a copper chelate or with more classical protecting groups. Protection of the phenol can be accomplished with the corresponding alkyl halide (e.g., BrZ, Doc) or with isobutylene ( Bu) [61,111-114] (Scheme 22). 

As an example, when the photoacid generator triphenylsulfonium hexafluoro-antimonate is exposed to radiation, it decomposes to release the superacid hexafluoroantimonic acid in the resist film. While this photochemical reaction can occur at room temperature, the acid-catalyzed deprotection of the pendant t-butyl group of the resist polymer occurs at reasonable rates only at elevated temperature. It is therefore necessary to heat the resist film to an appropriate temperature (PEB) to provide the energy that is required for the acid-catalyzed deprotection of the t-butyl group of the ester, which in mrn affords the base-soluble norbomene carboxylic acid unit the isobutylene volatilizes. The extent of deprotection at constant temperamre is dependent on the dose of applied radiation. By monitoring the carboxylic acid OH stretch 3000-3600 cm and the ester carbonyl (C O) around 1735 cm acid carbonyl (C O) around 1705 cm , and ester (C-O-C) stretch around 1150 cm it is possible to determine by means of IR spectroscopy the extent of dose-dependent deprotection, as well as the influence of baking temperature on the extent of deprotection for each resist system. Doses ranging from 0 to 50 mJ/cm were applied to each resist system, after which they were baked at 120, 130, 140, and 150°C for 60 seconds and analyzed by FTIR. ... 

Figure 11.20 shows the dose-dependent absorbance profiles of the carboxylic OH stretch (3100-3500 cm ) and the ester C-O-C stretch (around 1150 cm of a poly(CBN-co-NBCA) exposed to 248-nm radiation and baked afterward at 120, 130, 140, and 150°C. The carboxylic acid OH stretch and the carboxylic acid carbonyl (C O) stretch (1695-1705 cm ) both increase, while the ester carbonyl (C O) stretch (1730-1735 cm ) decreases with increasing dose of exposure (0-50 mJ/cm ), which allows us to follow the deprotection of the t-butyl ester group and the consequent conversion to a carboxylic acid group. The C-O-C (1150 cm ) stretch of the ester also decreases with dose of exposure, indicating the loss of the isobutylene group from the resist polymer. ... 

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