Tertiary organization

Acryhc esters dimerize to give the 2-methylene glutaric acid esters catalyzed by tertiary organic phosphines (37) or organic phosphorous triamides, phosphonous diamides, or phosphinous amides (38). Yields of 75—80% dimer, together with 15—20% trimer, are obtained. Reaction conditions can be varied to obtain high yields of trimer, tetramer, and other polymers. 

Cellulose sulfated usiag sulfamic acid degrades less than if sulfated usiag sulfuric acid (23). Cellulose esters of sulfamic acids are formed by the reaction of sulfamyl haHdes ia the presence of tertiary organic bases (see Cellulose esters). 

In absence of diluent, quatemation of some tertiary organic bases may proceed explosively. 

The solvent process involves treating phthalonitrile with any one of a number of copper salts in the presence of a solvent at 120 to 220°C [10]. Copper(I)chloride is most important. The list of suitable solvents is headed by those with a boiling point above 180°C, such as trichlorobenzene, nitrobenzene, naphthalene, and kerosene. A metallic catalyst such as molybdenum oxide or ammonium molybdate may be added to enhance the yield, to shorten the reaction time, and to reduce the necessary temperature. Other suitable catalysts are carbonyl compounds of molybdenum, titanium, or iron. The process may be accelerated by adding ammonia, urea, or tertiary organic bases such as pyridine or quinoline. As a result of improved temperature maintenance and better reaction control, the solvent method affords yields of 95% and more, even on a commercial scale. There is a certain disadvantage to the fact that the solvent reaction requires considerably more time than dry methods. 

Secondary and tertiary organic radicals (see p. 207) cannot be completely developed vertically... 

Thiophene-2-carbaldehyde condenses easily with ethyl acetoacetate or ethyl nitroacetate in the presence of TiCU and a tertiary organic base (pyridine or N- methylmorpholine) at 0-22 °C, giving (361) (72T663). Base-catalyzed condensation of thiophene-2-carbaldehyde with methyl (methylthio)methyl sulfoxide followed by treatment with HC1 in alcohols gives (2-thienyl)acetic esters (Scheme 114) (79BCJ2013). 

The properties of silicomolybdic acid are like those of silicotungstic acid. Toward indicators having a pH of 5 to 6 it behaves as a tetrabasic acid. With phenolphthal-ein as the indicator it requires eight equivalents for titration in cold solution but twenty-four equivalents for titration at 100°C. With tertiary organic bases it is tetrabasic. 

The salts formed with tertiary organic bases represent the neutralization of four hydrogens. Hence by some the acid is considered to be tetrabasic, whereas others consider it to be octobasic.5 Perhaps it is best to consider the tetra-substituted salt the normal one and the octo-, a basic salt. 

Dehydrohalogenation of substituted acetyl chlorides via tertiary organic bases and the stereoselective construction of an azetidinone ring from an imine (the Staudinger reaction) has played an important part in the development of azetidinone chemistry, which has been reviewed <1993MI637>. The use of bicarbonates in the presence of a crown ether at — 10°C has been suggested as an economical alternative to tertiary amines <2003SL1937>. 

Example 7.5. Olefin hydrvformylation with paraffin by-product formation [7,9]. Hydroformylation of olefins to aldehydes, catalyzed by a phosphine-substituted cobalt hydrocarbonyl, HCo(CO)3Ph (Ph = tertiary organic phosphine), has been used for illustration in examples 5.2 and 5.3 in Sections 5.2 and 5.3. The catalyst also promotes hydrogenation, so aldehyde produced from olefin is converted to alcohol, and paraffin is formed from olefin as by-product ... 

Example 8.3. Phosphine-substituted cobalt hydrocarbonyls as hydroformylation catalysts. Extensively studied catalyst systems with complex equilibria include phosphine-substituted hydrocarbonyls of cobalt, HCo(CO)3Ph, where Ph stands for a tertiary organic phosphine. They are modifications of the original oxo catalyst, HCo(CO)4. Like the latter, they catalyze the oxo or hydroformylation reaction of olefins to aldehydes one carbon number higher ... 

Higher aliphatic esters of starch are generally prepared by treating starch with the acid chloride in the presence of alkali or a tertiary organic base " such as pyridine, " quinoline, picoline," or dimethylani-... 

Cellulose acetate phthalate is produced by reacting the partial acetate ester of cellulose with phthalic anhydride in the presence of a tertiary organic base such as pyridine, or a strong acid such as sulfuric acid. 

The palladium catalyzed reaction between a terminal alkyne and an unsaturated organohalide or organotriflate in the presence of Cul and a tertiary organic amine is the... 

The cyclization reactions of various hydrazino substituted nuclei have been studied especially by American 6, 223) and Japanese Workers 186, 316, 320). The condensations are usually carried out in tertiary organic bases such as pyridine, quinoline, triethylamine or with sodium... 

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