Acid startg

A soln. of 20 g. (-)-a-sant(/nin in dry tetrahydrofuran added to liq. NHg, small pieces of Li added with stirring during 10 min., allowed to stand 15-20 min., then solid NH4CI added portionwise during 10 min. to disdiarge the blue color 16 g. 3-oxoeudesm-4-en-12-oic acid (startg. m. f. 242). V. M. Sathe and A. S. Rao, Indian J. Chem. 9, 95 (1971) s. a. Synth. Meth. 18, 65 suppl. 27. 

A soln. of diethyl y -cyanomethylglutarate in coned. HCl heated 45 min. on a water bath at a bath temp, of 85-90°, cooled, water added, and coned, in vacuo at a temp, as low as possible glutarimide-/ -acetic acid (startg. m. f. 625). Y 80.2%. Y. Egawa, M. Suzuki, and T. Okuda, Ghem. Pharm. Bull. 11, 589 (1963). 

A cold soln. of HNOs in propionic acid added at 0° to a soln. of 6gm. 3-methyl-4-(morpholinylmethyl)-2,5-diphenylfuran in propionic acid, and worked up after 20 min. —y 6 gm. crude l,2-dibenzoyl-l-methyl-2-(morpholinylmethyl)ethylene (startg. m. f. 5, 229). (P. S. Bailey and G.Nowlin, Am. Soc. 71, 732 (1949).)... 

A soln. of 3 gm. a-phenacylpyridine oxime in abs. ether shaken while gradually treated with no more than 3 gm. of PCI, shaking continued for 3 hrs., then made faintly alkaline with K2C0s — crude a-pyridylacetic acid anilide (Y 90%) dissolved in abs. alcohol, HCl-gas passed in, and boiled 3 hrs. —ethyl a-pyridyl-acetate (startg. m. f. 356) (Y 80-85%). (F. Galinovsky and G. Kainz, M. 77, 137 (1947).)... 

A soln. of l-keto-l,2,3,4-tetrahydrophenanthrene in acetic anhydride treated dropwise -with swirling in an ice bath with a soln. of coned. H2S04 in acetic anhydride, allowed to stand 2 hrs. at room temp., worked up, and the process repeated - l-keto-l,2,3,4-tetrahydrophen-anthrene-2-sulfonic acid hydrate (startg. m. f. 183). Y 85%. (F. e. s. C. Djerassi, J. Org. Chem. 13, 848 (1948).)... 

A 36%-formaldehyde isoln., followed by benzenesulfonyl chloride over a period of 45 min., added with stirring and cooling to an almost satd. aq. KCN soln., and stirring continued for 1 hr. -> (O-phenylsulfonyl)-glyoolie acid nitrile (startg. m. f. 472). Y 80%. (F. e. s. J. Lichten-berger and C. Faure, Bl. 1948, 995.)... 

A mixture of N-tosyl-/ -anilinopropionic acid and PC15 in dry thiophene-free benzene refluxed for 80 min., cooled to 0 in an ice-bath, anhydrous SnCl4 in thiophene-free benzene added, after 5 min. at 5° allowed to stand 12 hrs. at room temp., and the complex formed decomposed with dil. HC1 -> N-tosyl-4-keto-l,2,3,4-tetrahydroquinoline (startg. m. f. 30 a). Y 95%.—The inverse Friedel-Crafts procedure with A1C13 (s. 652) had to be used in other cases. (W. S. Johnson, E. L. Woroch, and B. Gr. Buell, Am. Soc. 71, 1901 (1949).)... 

Methoxy-2-(2-naphthyl) benzoic acid warmed 1 hr. at 60-80° with 3 parts of S0C12 —> 4-methoxy-7,8-benzofluoren-9-one (startg. m. f. 64). Y 91%. (H. Richtzenhain and A. Micdreich, Chem. B. 81, 92... 

Startg. a-isonitrosoketone allowed to react with H2SO4 in moist acetic acid imide. Y 16%. E.R.H. Jones et al., Chem. Commun. 1968, 210. 

Startg. bromolactonecarboxylic acid heated 1 hr. at 150-160 in a sealed tube -> product. Y 66%. - This is part of a simple stereospecific synthesis of dl-muscarine. Also formation of a 2,5-/rfln5-compound s. T. Matsumoto, A. Ichihara, and N. Ito, Tetrah. Let. 1968, 1989. 

A suspension of the startg. diketoenamine in 10 parts polyphosphoric acid heated 1.5 hrs. on a steam bath with occasional stirring 2-methyl-l,6-diphenyl-4-pyri-done. Y 95%. F. e. s. S. Boatman et al., J. Org. Chem. 52, 3817 (1967). 

Startg. hydroxyamide dissolved during ca. 1 hr. in ice-cooled coned. H2SO4, and the product isolated after another hr. 2-methyl-3-phenyl-3,4-dihydroisocarbo-styril. Y 86%. F. e., also in acetic acid containing H2SO4, s. C.-L. Mao, I. T. Barnish, and C.R. Hauser, J. Heterocyclic Chem. 6, 83 (i969) Can. J. Chem. 47, 3671 (1969). 

Hydroazulenes. Startg. trans-iustd. ketotosylate refluxed with 2 equivalents K-ace-tate in glacial acetic acid -> product. Y 78%. C. H. Heathcock and R. Ratcliffe, Chem. Commun. 1968, 994. 

Mercaptoquinoline ring. Startg. thioamide heated 20 min. at 110-120° with poly-phosphoric acid 4-mercapto-6-methoxy-2-phenylquinoline. Y 85-90%. F. e. s. J. Moszew and J. Zawrzykraj, Zesz. Nauk. Univ. Jagiellon., Pr. Chem. 7967, No. 12, 13 (Pol) C. A. 69, 18991. 

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