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3,5-Dimethoxy-6-chloromethyl-4-methylphthalide has been produced from 3,5-dimethoxy-p-toluic acid by heating with aqueous formaldehyde and hydrochloric acid. A chloromethylphthalide has been produced in a similar reaction from 5-methoxy-m-toluic acid, but its orientation has not been established. By treatment with potassium cyanide followed by hydrolysis this chloromethylphthalide has been changed to a phenylacetic acid. Oxidation with permanganate has opened the phthalide ring giving a tricarboxylic acid.When 5-methoxy-p-toluic, 5-methoxy-o-toluic, and 3,5-dimethoxy-o-toluic acids respectively are treated with formaldehyde solution and hydrochloric acid, the normal phthalides are produced. This conclusion has been verified by comparison with phthalides produced from the same acids by the Fritsch method. Hydrobromic or hydriodic acid may replace hydrochloric acid in these reactions. Attempts to employ aliphatic aldehydes other than formaldehyde in the reaction have been unsuccessful owing to polymerization of the aldehydes.

3-AAcetamido-and 3-amino-fluoranthene are brominated in the 2-position. Two new fluoranthene compounds are reported: 2-bromo-3-acetamidofluoranthene and 2-bromofluoranthene. The theoretical implications of these results are discussed.

The products of the condensation of 5-methoxy-3-methylbenzoic acid with aqueous formaldehyde and hydrochloric acid in the presence of glacial acetic acid are dependent on the length of the heating period. .A very short period of heating (2 minutes) yields 6-methoxy-4-methylphthalide and the two chloromethylphthalides of m.p. 135' and 154' C, related to the unisolated 4-methoxy-6-methylphthalide. If the period of heating is 20 minutes or longer, the above chloromethylphthalide melting a t 135' is formed and in addition some of the 6-methoxy-4-methylphthalide is chloromethylated to 6-methoxy-7-chloromethyl-4-methylphthalide, melting a t 179'. The orientation of all three chloromethylphthalides has been established. INTRODCCTIOUIn 1945, Charlesworth et al. (I) reported the isolation of two products from the condensation of 5-methoxy-3-methylbenzoic acid (I) with formaldehyde and concentrated hydrochloric and acetic acids. Of these, the compound which melted a t 176-178' C was established as a chloromethylphthalide, but its orientation was not proved. The present paper establishes the orientation of this and other products isolated in this reaction.The phthalide ring may form in two ways to produce the simple phthalides I1 and 111.On further reaction a chloromethyl group may enter positions 5 or 7 in I1 or 5 or 7 in 111.Thus, four chloromethylphthalides (IV-VII) are theoretically possible. All condensations were carried out using the Edwards, Perkin, and Stoyle (2) method as modified by R%y and Robinson (3) by the addition of glacial acetic acid to the formaldehyde -hydrochloric acid mixture. The length of the heating period determined the number and nature of the products isolated. When the mixture was heated for 2 minutes or less, that is, just for the length of time to put everything into solution, only the simple phthalide I1 and the chloromethylphthalides VI and VII were formed. The chloromethylphthalide IV, m.p. 178-179' C, of the earlier paper was not formed under these conditions. I t was formed along with I1 and VI if the condensation time was extended to 20 minutes or more. I t (IV) can also be formed alone from phthalide I1 in continued condensation of 20 minutes or more. Phthalide I11 was not isolated from any of the condensations and apparently is chloromethylated as fast as produced.The orientation of phthalide I1 was established by mixed melting point and infrared spectra comparison with this phthalide produced by the Fritsch reaction. RIeldrum (4) synthesized and established the orientation of both the simple phthalides by this method. When phthalide I11 formed by the Meldrum method was subjected to further chloromethylation VI and VII are produced, but not IV. Thus, chloromethylphthalides VI and VII have been proved to be related to phthalide 111, and IV, as previously, to phthalide 11. In establishing the orientation of the three isolated chloromethylphthalides it was thus necessary to determine the orientation of IV (or V) as derived from the simple phthalide I1 and one of the two chlorom...

Nitration of 3-nitrofluoranthene yields 3,9-dinitrofluoranthene, and nitration of 2-acetamidofluoranthene yields 2-acetaniido-3-nitrofluoranthene. The orientation of both these compounds has been proved. Nitration of 2-nitrofluoranthene has given a dinitro product, but its orientation has not been established. A number of other new fluoranthene derivatives are described.