Gilman test

Ti(CH3)3 [32835-60-2] Ti(lII) trialkyl not isolated green solutions give positive Gilman test ... 

The addition of the organolithium solution is continued until a positive Gilman test is obtained. 

Complete reaction of the alkyllithium can be tested by means of the Gilman test described in Expt 5.8, Note (3). 

If Cl is substituted for I, no reaction occurs in ether or THF. The authors postulate that a surface-mediated reaction takes place, and because no positive Gilman test occurs, no intermediate Grignard reagent is formed. 

As for a Grignard reaction the Gilman test (page 879) can be used to determine the conclusion of the reaction. 

Prepare 3,5-dimethoxybenzoic acid as described elsewhere here, and to a solution of 18.2 g in 250 ml dry tetrahydrofuran under N, add 1 g 85% LiH, stir for fourteen hours and then reflux for one-half hour. Add a solution of about 1.3 M butyllithium in ether (Org. Rxns. 6,352(1957)) with stirring and ice cooling until the reaction mixture gives a positive Gilman test (JACS 47,2002(1925)). Then add 500 ml ice water, extract with ether and dry, evaporate in vacuum the organic phase to get a yellow oil which is dissolved in an equal amount of absolute ethanol left in refrigerator twelve hours to precipitate. Filter and evaporate in vacuum the ethanol to one-half volume to give more precipitate for a total of 18 g l-(3,5-dimethoxyphenyl)- pentanone (I). 5.64 g (I) in 200 ml methanol ... 

The Gilman test (38), a color test for the detection of a Grignard reagent, is performed on each preparation prior to its use in the synthesis of C-palmitic acid. First, 0.5 mL of the Grignard solution is treated at room temperature with an equal volume of a 1% solution of 4,4 -bis(di-methylamino)benzophenone (Michlers ketone) while shaking. The... 

Gilman test 0.5-1 ml. of the test solution is reacted at room temperature with an equal volume of a 1% solution of Michler s ketone (di-p-dimethylaminophenyl ketone) in dry benzene. After a few minutes, 1 ml. of water is carefully added with shaking. The resulting solution, which may have to be filtered, is tested with a few drops of a 0.2% solution of iodine in acetic acid. A characteristic greenish-blue color appears in the presence of Grignard reagent. [)l. Gilman and G. Schulze, J. Amer. Chem. Soc. 2002 (1925).]... 

Cyclopropanol ring. Ethereal iV butyllithium soln. added dropwise at room temp, to ethereal exo/eiido-7-bicyclo[4.1.0]heptyl y5-chloroethyl ether until the Gilman test (s. Synth. Meth. 13, 789) is positive, then poured into satd. NaHC03-soln. -> exo/endo-7-hydroxybicyclo[4.1.0]heptane. Y 94%. F. e. s. J. Paust and U. Schollkopf, Ang. Gh. 77, 262 (1965). 

Ethereal methyllithium soln. added at -15 under argon to anhydrous cuprous iodide in ether, after a negative Gilman test is obtained methyl 10-acetoxy-3,7,ll-trimethyl-2-trafi, 6-trfl/w-ll-dodecatrienoate in ether added, and the product isolated after 1 hr. at -10 methyl 3J,ll-tnmQthyl-2-trans,6-trans,10-trans- tridecatrienoate. Y 87% purity 93%. F. e. s. R. J. Anderson et al.. Am. Soc. 94, 5379 (1972). 

Trimethylpyrylium perchlorate added in small portions under Ng to G>-styrylmagnesium bromide in anhydrous ether so that the temp, does not rise above —25°, stirring continued ca. 10 min. until the Gilman test is negative4,6-dimethyl-8-phenylocta-3,5,7-trien-2-one. Y 53-60%. F. e. s. G. Kobrich and D. Wunder, A. 654, 131 (1962). 

Anhydrous GdGlg added cautiously to n-butylmagnesium bromide in ether, refluxed 1 hr. with stirring until the Gilman test (s. Am. Soc. 47, 2002 (1925))... 

Deep red-brown soln., negative Gilman test (g, h) White cryst., m. 180-9T soly. m. 156 , monomeric (i)... 

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