Grundmann method

Finally, mention should be made of the Grundmann method which, though long winded and unlikely to be of use today, was once of some importance. It is summarized in Scheme 9. In favorable cases the sequence could be carried through in over 50% overall yield, and it was valued for its ability to synthesize aldehydes inaccessible via the classical Rosenmund. 

For aliphatic hydrocarbons in the medium range (7-12 carbon atoms), which are not satisfactorily amenable to either the Hass or the Grundmann method, Geiseler154 has described a process of nitration by nitrogen dioxide under pressure, for which the overall reaction is ... 

The potential of the reaction of nitrile oxides with alkynes was already recognized at the time of the earlier review.1 The realization of that potential was apparent 7 years later in the comprehensive account by Grundmann and Griinanger.59 In Table II we list a selection of the syntheses reported in the period 1970-1978, illustrating new applications of the method and some of the generalizations discussed.59,71,84,89,91-100... 

C. Grundmann, in Newer Methods in Preparative Organic Chemistry (W. Foerst, ed.), Vol. 5, pp. 176-210. Academic Press, London and New York, 1968. 

G. Grundmann, Newer Methods of Preparative Organic Chemistry, Interscience, New York, 1948, p. 103. 

Ross, 1962 Rotz and Grundmann, 1957 LaBrecque, 1961). They are prepared by the general method of synthesis of phosphoroamidates and phosphorothio-amidates. 

Grundmann s aldehyde synthesis also starts from acid chlorides. The latter are converted by way of the diazo ketones or acetoxy ketones into the glycols, which are subjected to cleavage by lead tetraacetate. <%,/ -Unsaturated aldehydes cannot be obtained by this method.457... 

This reaction was initially reported by Grundmann in 1936. It is the conversion of acyl chloride into aldehyde with the exact same carbon skeleton via the following consecutive steps a) treatment of acyl chloride with diazomethane to form a ketone, (b) conversion of such a ketone into ketol acetate with acetic acid, (c) reduction of ketol acetate with aluminum isopropylate, and d) hydrolysis and oxidation with lead tetraacetate. This method is especially useful in the preparation of aliphatic aldehydes with methylene-interrupted double bond(s). Although polymers might form in the preparation of highly unsaturated aldehydes during the reduction with aluminum isopropylate, the reduction from lithium aluminum hydride can eliminate such drawbacks. ... 

Trimethyl phosphite added to a soln. of 2,4)6-trimethoxybenzonitrile oxide in benzene, and heated 5-10 min. on a steam bath 2,4,6-trimethoxybenzonitrile. Y 93%. — This is a mild and generally applicable method. F. e., also with other phosphorus (III) compounds, s. G. Grundmann and H.-D. Frommeld, J. Org. Ghem. 30, 2077 (1965) reduction with isonitriles cf. P. Vita Finzi and M. Arbasino, Tetrah. Let. 1965, 4645. 

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