The synthesis of 2-methyl butanal by reaction of n-butyl isocyanide with secondary-butylcadmium bromide, pt. 1 : a study of the reactions between carbon monoxide and the sodium salt of nitroethane, pt. 2 by John M Bruce Jr A THESIS Submitted to the Graduate Committee in partial fulfillment of the requirements for the degree of Master of Science in Chemsitry at Montana State College Montana State University © Copyright by John M Bruce Jr (1949) Abstract: Part I. 2-methyl butanal was prepared by the following sequence of reactions: [Formulas not Captured by OCR] A light yellow liquid was obtained as product. Confirmatory tests were run using small portions of the final product, and close agreement was found to exist between these results and the actual data pertaining to 2-methyl butanal. The 2,4-dinitrophenylhydrazone derivative was prepared from the final product, and its melting point determined. Experimental details of the above procedure ere presented, along with an explanation of the experimental results. Part II A reaction mixture consisting of the sodium salt of nitroethane and nickel carbonyl in a solvent of cyclohexane, was subjected to high pressures of carbon monoxide. This reaction mixture yielded, upon hydrolysis, a substance possessing a solubility which could not readily be accounted for. This substance is not obtained in the absence of nickel carbonyl, or when cyclohexane itself is subjected to carbon monoxide under pressure in the presence of nickel carbonyl. The unidentified substance is decomposed by steam distillation, simple distillation, and vacuum distillation, and cannot be crystallised satisfactorily even at low temperatures. Positive Schiff's and Tollen's tests were obtained by use of the appropriate reagent and the unknown substance. Derivatization of the unidentified material has not been possible. Additional investigation of the unidentified substance is being conducted. Part I, ©B SBWSSIS # S-MIS'SHYS %mmj& S i HBAefIOH OS n-BUflf ISO- OWIBB VIfK #COmA#-I%%leABBID% BBCMim, Paft II. A SfGDY Qf BBB BBAGfIOBS KBfMBBB OARBQP MQB9&%9% AHD %BB SODIGB sutize op mgaoEmAmi. % ',JOBS M> BvBGOB,' A fHBSlS • ’ ; ’ submit to the Graduate Oomslttea ,. partial fulfillment- Of the requirements for the decree of Master of Science in Chemistry a t Montana State. College Approyedt "'I'WWjIlO.' HI.U' Head of Major Department Chairman, Examining Committee ifean^G-H^duate^risioft Bozeman, Montana June 1949 - 2 - TABLE Of CONTENTS Sg- i m I - I . ABSTRACT ........................... 4 I I . INTRODUCTION .................. 5 I I I . theoretical discussion 7 IV. experimental .................. 10 S ilv e r cy en ld e. ........................... 10 n-Butyl leocysntde .......................... 10 Secondsry-butylms»neeIum bromide 11 Secondsry-butylcedmlum bromide. 12 Synthesis of 2-methyl bntenel . 13 Tests of confirmation .................. 14 Preperetlon of the derivative , 16 V. DISCUSSION OP EXPERIMENTAL RESULTS 18 VI. SUMMARY......................................................... 20 PART H . I . ABSTRACT...................................................................... 21 I I . INTRODUCTION...................................................................................................... 22 I I I . THEORETICAL DISCUSSION................................................................................ 23 IV. EXPERIMENTAL ................................................................................ 2? A p p p re tu s ............................................................................................ 27 Preppretlon of the sodium salt of nit roe then# .................. 28 !typical procedure for experimental ru n s ................................. 29 8 9 3 " 3 (Table of Contents ) - 3 - JaS- A. Effect of Variations In Procedure on Yield of Product . 31 (1) E e e t ..............................................................................................................31 (2) Omission o f N ickel C arbonyl.........................................................31 (3) Omission of S a l t ............................................................. 31 (b) Use of Salt containing methyl alcohol........................................ 31 (5) In presence of hydro .............................................................................32 (6) Hydrolysis of run previous to pressuring with carbon monoxide .................................. 32 (?) V a ria tio n s in p r e s s u r e ..................................................................33 B. Attempts at Purification of Layer B ........... 33 (1) D is tilla tio n a t o rd in ary p re s s u re ........................................... 33 (2) Vacuum distillation. ...... ....................................... 3^ (3) Steam distillation .......................................................................... 3^ (h) C ry s ta lliz a tio n a t Low T e m p e ra tu re .............................................35 C. Attempts to Identify Layer B and Prepare Derivatives. 35 (1) Schiff*s end Tollen1 s T est .......................... ..............................35 (2) 2,U-dInltrophenyIhydrazIne and semlcarbazlde hydro­ c h lo rid e .................................. 35 (3) Schiff1 s Base Formation. .................................................................. 36 (b) Acetal formation ....................................................................................3& •(5) O xid atio n .................................................... 36 (6) Reduction .................................. 38 D. A Reaction Involving the Salt of 2-Nitropropene ...........................38 V. DISCUSSION Of EXPERIMENTAL RESULTS............................................... 40 VI. SUMMARY.......................................................................................................................... 42 V II. ACKNOWLEDGMENT.............................................................................................................4-3 V III. LITERATURE CITED AND CONSULTED......................................................................44 — ^4- — I* abstract £zrk I. 2- methy I buteneI wee prepsred by the following sequence of reectlone: H CH1CH2CH2CH2N=C + CH1CH2-IJHCdBr Br H H A light yellow liquid was obtained se product. Confirmatory tests were run using email portions of the final product, end close agreement wee found to exist between these results end the actual data pertaining to 2-methyl butaneI. The 2fb-dinitrophenylhydrezone derivative was pre­ pared from the final product, and Its melting point determined. Experimental details of the above procedure are presented, along with an explanation of the experimental results. - 5 - J I . INTRODUCTION The ieocypnldes, or cerbylemlnee, RNC, exist me colorless liquids, which pre insoluble In weter, end hpve a pp rtlculfrly disagreeable odor. The vapors are very toxic, capable of causing dizziness end vomiting If in­ haled over a sufficient period of time. The cerbylemlnes are very reactive compounds. Some general reactions involving I so cyan idee and other molecules are listed by Nef^ Oilmen^ ^ , and Cohen^^. It has been demonstrated that the Isocyanide group enters into an addition reaction with the Orignerd reagent; it else enters into reactions with sulfur and chlorine at temperatures above IOO0C1 with the formation of HNCS and ENCtCljg, respectively. Furthermore, it adds acid c h lo rid e s to give alkyllm ldo c h lo rid e s, HNiC(Cl)COR. Sachs and Loevy^?) give the complete procedure for the preparation of benzaldehyde by a reaction involving phenylmagnesiua bromide and methyl Ieo- cyanlde. No other aldehydes are reported to have been synthesized by this method. On the baeis of the results obtained from attempted interaction between phenylmagneslum bromide end various alaphatic and aromatic Iso- (o) cyanides. Oilmen and Heckert concluded that only methyl lsocyanide wee of sufficient reactivity to combine with the Orignard reagent. The desirability of developing.the method of Sachs and Loevy into a good aldehyde synthesis is apparent, since aldehydes are the starting materials from which a large number of important compounds may be made. The selection of the orgenocedmlum compound as sn alternative orgsno- m etallie compound was prompted by the conclusions drawn from the experi­ mental work of Oilman and Nelson^ and de Bonneville^. These workers found that the relatively lower reactivity of the orgpnocadmium compounds caused the arresting of subsequent harmful interaction between the products formed during an in itial stage. Inasmuch as organometallic compounds differ generally in degree or rate of reaction, rather than in kind, it was assumed that the organocadmlua compound would add to the ieocyanlde group in a manner similar to that of the Grignard reagent. It was hoped that a single addition product would result from the reaction between the eerbylamine and the organocadmium compound. Oilman and M elson^^ have treated the subject of organometallic compound preparation quite extensively; however, some disagreement exists (<) between these men and Cason J with regard to the stability of organo­ cadmium compounds et elevated temperatures. According to the letter, the organocadmium compounds can be prepared at room temperature without decom­ position of the product, while Gilman and Nelson state that a cooled reaction mixture is necessary to prevent decomposition. Cason's procedure was the one used in the preparation of the organocadmium compounds in thle work. n-Butyl isocyanide was selected