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A Study of the Reactions of Carbon Monoxide with B-Dicarbonyl

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A study of the reactions of carbon monoxide with B-Dicarbonyl compounds and their derivatives [and] the synthesis of aldehydes by the reaction of formyl fluoride with organocadmium bromides by Jack R Gaines A THESIS Submitted to the Graduate Committee in partial fulfillment of the requirements for the degree of Master of Science in Chemistry Montana State University © Copyright by Jack R Gaines (1950) Abstract: The reactions between carbon monoxide and the metal enolates of β -di-carbonyl compounds have been investigated. The catalysts used were nickel tetracarbonyl and dicobalt octacarbonyl. Hydrogen was used, in many cases, in addition to the carbon monoxide. Reactions were also run with the free β -dicarbonyl compounds. No apparent reaction was found to take place between carbon monoxide and these compounds under the conditions which were used. The reaction of O-acetylacetoacetic ester with carbon monoxide and hydrogen in the presence of dicobalt octacarbonyl, however, led to the synthesis of an aldehyde. The identity of this aldehyde has not yet been determined. Experimental details are given on the preparation of formyl fluoride and the synthesis of 2-methyl-l-butanal by the reaction of formyl fluoride with secondary-butylcadmium bromide. The synthesis of other aldehydes by using formyl fluoride and organocadmium compounds is mentioned. A STbW OP RiSAOTIOKg OIF OARBOR 'M DRGIim R IT g /J-DIOARBQIiIL COSSFOUHDg MB TliElS D:%I7ATI7ES* T m .G W m g is o r ALDEmmEg m T m E m c T s m o ? mam, mmmm -,smi oRcmocAiamm BRo&EDEg, Jack E, Caines . A TRBSIg - , - Sabmitted to the Graduate Committee i n partial AlfilIment of the reqhiremente for the degree of laster of Science, in Chemistry . at Montana. State College Approved; Boaemanj Montana ,Tular 1950 Q-ILs C f-f3, Zj — 2 — TABLIj OF CONTENTS I . ABSTRACT.......................................................................................................... 4 I I . INTRODUCTION ................................................................................................ 5 I I I . THEORETICAL DISCUSSION ........................................................................ 7 IV . EXPERIMENTAL................................................................................................ 11 M a te r ia ls ........................................................................................... 11 A p p a ra tu s ........................................................................................... 11 Dicobalt octacarbonyl .............................................................. 11 Sodium a c e t o a c e t ic e s t e r ..................................................... 12 Sodium a c e ty la c e to n e . .......................................................... 13 C opper a c e t o a c e t ic e s t e r ..................................................... 13 Copper acetylacetone .............................................................. 13 Zinc acetylacetone ................................................................... 14 O - A c e ty la c e to a c e tic e s t e r ..................................................... 14 Reaction of acetoacetic ester vdth carbon monoxide and hydrogen .... ............................................................ 15 Reaction of acetylacetone with carbon monoxide 15 Reaction of acetylacetone with carbon monoxide Jfw and h y d r o g e n .................................................................................. 15 Reaction of sodium acetoacetic ester with carbon m onoxide ........................................................................................... 15 Reaction of sodium acetylacetone with carbon m o n o x i d e ......................................................... ................................. 17 Reaction of zinc and copper acetylacetone with carb o n m onoxide and hydrogen ................................................ 17 Reaction of O-acetylacetoacetic ester with carbon monoxide and hydrogen ........................................... 17 -T CM 94725 (Table of Contents) PKt Preparation of formyl fluoride ..... ....................................... 19 Seoondary-butylm: £ae slum bromide ......................................................... 20 Secondary-butylcadiidum bromide .............................................................. 20 S y n th e s is o f S - m e th y lb u ta n a l- l .............................................................. 21 Reactions of fori«iyl fluoride witn other organoeadmium bromides ................................................................................. 22 V. DISCUSSION OF EXPERIMENTAL RESULTS.................................................................. .. ; V I. SUKLURY................................................................................................................................ 24 V II. ACKNOWLEDGMENT................................................................................................................. 25 V I I I . LITERATURE CITED AND CONSULTED........................................................................... 26 - 4 - I l ABSTRACT The reactions between carbon monoxide and the metal enolates o f -d i­ carbonyl compounds have been investigated. The catalysts used were nickel tetracarbonyl and dicobalt octacarbonyl. Hydrogen was used, in many cases, in addition to the carbon monoxide. Reactions were also run with the free /6 -d icarbonyl compounds. No apparent reaction was found to take place between carbon monoxide and these compounds under the conditions which were used. The reaction of O-acetylacetoacetic ester with carbon monoxide and hydrogen in the pre­ sence of dicobalt octacarbonyl, however, led to the synthesis of an alde­ hyde. The identity of this aldehyde has not yet been determined. Experimental details are given on the preparation of formyl fluoride and the synthesis of 2-methyl-l-butanal by the reaction of formyl fluoride with secondary-butylcadmium bromide. The synthesis of other aldehydes by using formyl fluoride and organocadmium compounds is mentioned. II. IN TH :-DTinTiaN The use of carbon monoxide as an addition reagent in organic syntheses has become of great technical importance. The number of types of compounds which may be synthesized by the use of carbon monoxide have been greatly increased within the past few years. The synthesis of methyl alcohol and higher alcohols from carbon mon­ oxide and hydrogen ^ ^ is carried out on a commercial scale. Both lab­ oratory and industrial reactions are knovn for the preparation of aldehydes, aliphatic and substituted aliphatic acids. The commercial production of acetic acid and its higher homologs by E.I. du Pont de Nemours ^ Is accomplished by the following reaction: BP3 +• H2O CH3OH + CO CH5COOH 75 atms., 125-180*0^ A sim ilar reaction between ethylene and carbon monoxide yields propionic acid C52) . By using various starting materials, hydroxy-acid:: , amino-acids ^ and polycar boxylic-acids ' have been produced by du Pont. Gattermami and Koch ^ - have shown that aromatic aldehydes can be prepared by the reaction of aromatic hydrocarbons with carbon monoxide and dry hydrogen chloride in the presence of anhydrous aluminum chloride and a small amount of cuprous chloride. Gutiike^,A)' has reported the synthesis of benzaldehyde by the reaction of benzene and carbon monoxide in the presence of anhydrous aluminum chloride and titanium tetrachloride at high pressures. Both inorganic ^ v'' and organic bases ^ will react with carbon monoxide, under pressure, to yield formates or other addition compounds. Two such reactions are: - 6 - KOH ( a q .) + CO ----- I^O 0Ct---- ^ HCOOK (98>) 20 atm . CH3OH + CO HCOOCH3 200-400 atm ? 7 0-10 0°C . Aldehydes have been synthesized industrially by reactions between carbon monoxide, hydrogen and olefins in the presence of cobalt catalysts and tinder conditions of high pressure ^ (31^ This process is known as the "oxo" process. Adkins and Krsek (Z) (3) have studied laboratory conditions under which certain unsaturated compounds w ill add carbon monoxide and hydrogen in the presence of dicobalt octacarbonyl. These reactions yield, in nearly all cases, a high percentage of a single addition pro­ duct. An illustrative example is given with allyl acetate: Ch2=Chch2 OOcch3 + co + h2 gow-loo^^/^s.i^ Ch3 Cooch2 Ch2 Ch2 Cho 110-125°c! The increasing importance of carbon monoxide as an addition reagent in organic syntheses was one of the reasons for the investigations con­ sidered in this paper. One of the original purposes of this investigation was the synthesis of aldehydes through the reaction of carbon monoxide and hydrogen with -dicarbonyl compounds or their derivatives. Formyl fluoride (Zl) is the only acid halide derivative of formic acid which has been isolated. It has been postulated that the hypo­ thetical formyl chloride is formed as an intermediate in the Gattermann- Koch synthesis of aromatic aldehydes (H ). Gilman and Nelson (13J have shown that organocadmium compounds w ill react with acid chlorides to form ketones. Ihus experiments were carried - 7 - out to determine the possibility of preparing aldehydes through the reaction of formyl fluoride with organocadmium compounds. I I I . THEORETICAL DISCUSSION No work, up to the present time, has been reported involving reactions of carbon monoxide and /S -dicarbonyl confounds or their metal enolates. Most of the work dealing with the reaction of an organic salt of any type with carbon monoxide, is that of sodium ethoxide and carbon monoxide. Stabler
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