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Synthesis and herbicidal activity of 1-ethynylcyclohexanol derivatives

M. Furdík, P. Rapoš, A. Štullerová, and S. Priehradný

Komensky University, Bratislava


Abstract: Starting from 1-ethylylcyclohexanol (I) and bis(1-hydroxycyclohexyl)acetylene (II), compds. IIa and IIb were prepd. and their herbicide activities were tested. IIa (X, R, m.p., or b.p., and % yield given): NH, Ph, 96-7°, 53 (III); NH, p-ClC6H4 (IV), 107-8°, 60.1; NH, m-ClC6H4 (V), 79-80.5°, 62; NH, m-ClC6H4 (VI), 118-19°, 70; NH, 2,5- Cl2C6H3 (VII), 84.5-5.5°, 63; O, Me (VIII), b16 110-12°, 64; O, Et (IX), b0.05 67-70° 58.5; O, Pr (X), b14 129-31°, 60.2; O, CH2CH:CH2 (XI), b17-18 132-5°, 75.7; (XR =) CH2Cl (XII), b0.01 59-61°, 63.5; (XR = CCl3) (XIII), b0.08 80-1°, 72.2. IIb (R', m.p., and % yield given): Ph (XIV), 191-2.5°, 64; m-ClC6H4 (XV), 205.5-207°, 61. An Et2O soln. of 0.5 mole tert-BuOK was satd. with dry C2H2 at -15° and simultaneously with passing C2H2 through the soln., a soln. of 0.5 mole cyclohexanone in 100 ml. abs. Et2O was added dropwise, and a stoichiometric amt. of aq. NH4Cl was added to liberate I. Distn. gave 76% I, b15 76.5-7°, together with 4.4 g., II, m. 109-9.5°. When C2H2 and Et2O soln. of 1 mole of cyclohexanone were simultaneously added to a soln. of 1 mole tert-BuOK in Et2O at -15° and the obtained mixt. treated with aq. NH4Cl, 53.2% II, m. 109-9.5° (C6H6, petr. ether) resulted. The compds. III-VII were prepd. as follows. To a soln. of 0.025 mole I in 5 ml., abs. C5H5N was added 0.025 mole corresponding phenyl isocyanate, the mixt. boiled 15 min., and then allowed to stand 2 hrs., at room temp. After pouring the mixt. into 40 ml. H2O with 5 ml. concd. HCl, the product was sepd. and recrystd. from n-hexane. Similarly were prepd. XIV and XV from II. Molar ratio of II to corresponding phenyl isocyanate was 1:2. The compds. VIII-XI were prepd. as follows. Na (1.1 g.) was dispersed in 50 ml., C6H6 and to this mixt. added dropwise during 20 min. at room temp. a soln. of 7.2 g. I in 10 ml. abs. C6H6. The Na salt of I was stirred 2 hrs., 0.055 mole of a corresponding chloroformate was added dropwise, the mixt. heated on a water bath 2 hrs., allowed to stand overnight, then washed with H2O, and the C6H6 layer sepd. and distd. XII and XIII were prepd. by treating I as follows. The appropriate acetyl chloride (0.1 mole) was added to a mixt. of 0.1 mole C5H5N in 90 ml. C6H6 at 0°, a soln. of 0.1 mole I in 30 ml. abs. C6H6 added dropwise during 15 min., the mixt. heated 1 hr. at 60°, cooled to -15°, the solid filtered off and washed with C6H6, the filtrate washed with aq. NaHCO3 to neutral reaction, and the C6H6 layer sepd., dried and distd. to give the product. Tests proved I to be the most active as a herbicide. The herbicidal properties of all the other compds. described were comparable with those of known herbicide standards 2,4-D (Agrion), Na salt of DNCK (Rafex), and CMU (Monuron).

Full paper in Portable Document Format: 179a616.pdf (in Slovak)


Chemical Papers 17 (9) 616–628 (1963)

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