Alicyclic anhydride

Ammonolysis of alicyclic anhydrides followed by Hofmann degradation is one of the most frequently used methods for the synthesis of alicyclic P-amino acids, since many anhydrides are commercially available cheap substances produced by Diels-Alder addition of maleic anhydride and the corresponding dienes [44], By this method, cis- and frans,-2-aminocyclohexane- and -cyclohexenecarboxylic acids, cis-2-aminocycloheptanecarboxylic acid [45], 3-ewtffo-aminobicyclo [2.2.1 ]heptane-2-ew/o-carboxylic acid, 3-e ifo-aminobicyclo[2.2.1 ]hept-5-ene-2-ertcarboxylic acid and some analogue P-amino acids have been prepared [44, 46-48], For partially unsaturated alicyclic compounds, a modified Hofmann degradation is used, sodium hypochlorite being applied to avoid bromine addition to the double bond [48,49]. 

A useful oxidizing reagent is silver(III) tristrifluoroacetate which can be generated from silver peroxide (AgO) and a tnfluoroacetic acid-tnfluoroacetic anhydride mixture [5f] This reagent readily oxidizes alicyclic and bicyclic hydro... 

Acetone cyanohydrin nitrate, a reagent prepared by treating acetone cyanohydrin with nitric acid-acetic anhydride, has been used for the At-nitration of aliphatic and alicyclic secondary... 

A solution of fuming or absolute nitric acid in acetic anhydride is another commonly used reagent for the V-nitration of V-alkylamides. Curry and Mason used this reagent to synthesize a series of aliphatic and alicyclic V-nitro-V-alkylcarbamates from the corresponding V-alkylcarbamates. Aromatic ring nitration is observed if aryl groups are present in the carbamate substrate. 

Aliphatic and alicyclic carbamates are nitrated smoothly and in excellent yields by a nitric acid-acetic anhydride mixture (4). Similarity, we have found that treating an acyl aliphatic amine and a urethane with one equivalent of nitronium tetrafluoroborate in acetonitrile at —30° C. gave the corresponding N-nitro derivatives in good to excellent yields. However, diacylamines are more difficult to nitrate, and Kauffman and Burger (9) have reported that nitrating succinimide required 13 hours... 

Although aliphatic and alicyclic hydrocarbons react with most sul-fonating agents, the reactions are not suitable for the preparation of the pure sulfonic acids. " Certain olefins react with sulfur dioxide-dloxane complex to give olefinic sulfonic acids In this way, cyclohexene is converted to l-cyclohexene-3-sulfonic acid, whereas with concentrated sulfuric acid in a mixture of acetic acid and acetic anhydride the main product is 2-hydroxycyclohexanesuIfonic acld. 1-Propene-l-sulfonic acid is obtained in low yield by the action of oleum on n- or isopxopyl alcohol. ... 

Another group of polymers with good heat resistance includes certain aryl-alicyclic compounds. They are generated from the polycondensation of 4,4 -diaminodiphenyl oxide with various anhydrides such as tricyclo[4,2,2,0 ]dec-9-ene-3,4,7,8-tetracarboxylic acid anhydride, 9-oxatricyclo[4.2,2,0 ]nonane-3.4,7,8-tetracarboxylic acid anhydride, cyclobutene-1,2,3,4-tetracarboxylic acid anhydride, and bicyclo[2,2,2]octane-23,5,6-tetracarboxylic acid anhydride. Thermal stability of these polymers is affected by the ring stability (strain) regardless the true chemical structure. Pyrolysis at 650° C generates some compounds that are the same in nature and some others that are characteristic for each polymer. The main decomposition paths, as indicated by the main pyrolysis products are shown below for each polymer (Ar = 4,4 -diphenylene oxide) ... 

Clemmensen reaction. The Clemmensen method of reduction (1913) consists in refluxing a ketone with amalgamated zinc and hydrochloric acid. Acetophenone, for example, is reduced to ethylbenzene. The method is applicable to the reduction of most aromatic-aliphatic ketones to at least some aliphatic and alicyclic ketones, to the y-keto acids obtainable by Friedel-Crafts condensations with succinic anhydride (succinolylation), and to the cyclic ketones formed by intramolecular condensation. 

Polymers for use in 193 nm lithography are co-, ter-, and tetra-polymers of 1) methacrylates, 2) norbornenes, 3) norbornene-maleic anhydride, 4) nor-bornene-sulfur dioxide, and 5) vinyl ether-maleic anhydride (Fig. 39). While 1), 3), 4), and 5) are prepared by radical polymerization, all-norbornene polymers 2) are synthesized by transition-metal-mediated addition polymerization [166-168].Norbornenes (Fig.40) are sluggish to undergo radical [168,169] and cationic [170] polymerizations. Their ring-opening metathesis polymerization (ROMP, Fig. 40) [ 171 ] has never produced worthy resist polymers. The C=C double bonds introduced in the ROMP polymer backbone must be hydrogenated to reduce the 193 nm absorption and the ROMP polymers tend to have low Tg. However, the major problem for the ROMP polymers was their unacceptable swelling in aqueous base development. While polymethacrylate systems contain etch-resistant alicyclic structures in the ester side chain, norbornene-based systems carry the alicyclic unit in the backbone. Essentially all the 193 nm re-... 

The reactions of alicyclic olefins with Se02 have been extensively investigated. Heating cyclopentene with Se02 in acetic anhydride (acylating oxidation) oxidizes it to much monoacetoxy- and a little diacetoxy-cyclopentene but in a bomb tube at 90-100° much diacetate and little monoacetate are obtained.225 Thus the second methylene group next to the double bond is more or less attacked according to the reaction conditions. 

Ring compounds containing carbon bridges are also formed by addition of, e.g., maleic anhydride to alicyclic dienes such as cyclopentadiene and cyclo-heptadiene of the two possible stereoisomers it is always the erafo-compound that is produced (Woodward-Hoffmann rules38). Such reactions, however, fail when the product would break Bredt s rule. 

Scheme 7.36 Synthetic scheme for the polymerization of norbornene and its derivatives via free radical polymerization (FRP), ring-opening metathesis polymerization (ROMP), and vinyl addition polymerization (VAP) techniques. Polymers I, II, and III are isomers that differ in their enchainment and physical properties. Co- and terpolymerization of norbornene and derivatives of norbornene with other alicyclic monomers such as maleic anhydride, methyltetracyclododecene carboxylic acid, etc. are also successfully synthesized with this scheme. (Note that 2, 3- and 2,7-enchainments of repeating units are reported in type I polymers. °°)...

Figure 7.16 SEM images of 150-nm line features printed in the first commercial version of the alicyclic polymer resist platform, based on poly(dinorbornene-a/t-maleic anhydride), and marketed under the brand name of ATOl by the JSR Corporation. Exposure wavelength was 193 nm.

Wallow, F.M. Houlihan, O. Nalamasu, E.A. Chandross, T.X. Neenan, and E. Reichmanis, Evaluation of cycloolefin maleic anhydride alternating copolymers as single layer photoresists for 193 nm photolithography, Proc. SPIE 2724, 355 (1996) F.M. Houlihan, T.I. Wallow, A. Timko, E. Neria, B. Hutton, R. Cirelli, O. Nalamasu, and E. Reichmanis, Recent advances in 193 nm single layer photoresists based on alternating copolymers of cycloolefins, Proc. SPIE 3049, 84 (1997) J. H. Park, S. J. Kim, S. Y. Park, and H. Lee, ArF photoresist system using alicyclic polymer, Proc. SPIE 3049, 485 (1997). 

Infrared spectroscopy provides a convenient method for studying the deprotection kinetics of resist polymers. For example, the deprotection kinetics of some alicyclic polymer resist systems comprising (i) poly(methylpropyl bicyclo[2.2.1]-hept-5-ene-2-carboxylate-co-bicyclo[2.2.1]hept-5-ene-2-carboxylic acid) (trivial name poly(carbo-t-butoxynorbomene-co-norbornene carboxylic acid) [poly(CBN-co-NBCA)] (I) and (ii) poly(methylpropyl bicyclo[2.2.1]hept-5-ene-2-carboxylate-co-maleic anhydride) (trivial name poly(carbo-t-butoxynorbomene-co-maleic anhydride) [poly(CBN-aZr-MAH)] (11) and containing triphenylsulfonium... 

Figure 17.9 The chemistry of the CARL process scheme. x may stand for hydroxystyrene, acrylates, and alicyclic monomeric units, etc. R represents an alkyl group. Structure (I) is the alkaline-insoluble resist resin, consisting of an alternating polymer of maleic anhydride and an appropriate monomer. Structure (II) is the product of the base-catalyzed hydrolysis of the anhydride resin. Structure (III) is the bis-diaminoalkyl-oligo-dimethylsiloxane, the CARL process silylating agent. Structure (IV) is the cross-linked product of silylating agent and the hydrolyzed anhydride resist resin.

The reactions of isatoic anhydrides with various nitrogen-containing compounds of the acyclic, alicyclic, and heterocyclic series leading to derivatives of quinazoline have been studied most widely. Here two approaches to the synthesis of compounds of this group were developed 1) The initially formed derivatives of anthranilic acid were converted in situ into the heterocyclic compounds 2) the derivatives were isolated and cyclized separately into the required products. For example, the amino derivative 109 was obtained with a yield of 56% by the first method with the action of ammonia followed by phosphorus oxychloride on a mixture of the anhydrides 107 and 108 [63],... 

The Wittig condensation has a wide range of applicability. The most suitable carbonyl components are generally aliphatic, alicyclic or aromatic aldehydes, but reactive phosphorus ylides also react with ketones, and even esters, amides and anhydrides can be reacted with phosphorus ylides in so-called non-classical Wittig reactions [13]. 

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