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SYNTHESIS OF TERTIARY ACETYLENIC ALCOHOLS DIBENZO-18-CROWN-6 FROM 4', 4"-DIAMINODIBENZO-18-CROWN-6
https://doi.org/10.29013/AJT-21-9.10-35-39
Kozinskaya Lyubov Konstantinovna, Lecturer, the Faculty of Chemistry National University of Uzbekistan E-mail: [email protected] Tadjiev Aziz Berdiyarovich, Master-2, the Faculty of Chemistry National University of Uzbekistan
SYNTHESIS OF TERTIARY ACETYLENIC ALCOHOLS DIBENZO-18-CROWN-6 FROM 4", 4""-DIAMINODIBENZO-18-CROWN-6
Abstract. Tertiary acetylenic alcohols dibenzo-18-crown-6 were synthesized by diazotization of 4', 4"-diaminodibenzo-18-crown-6 followed by nitrogen evolution, the main characteristics of the structures and the data of 1H- and 13C-NMR spectra are given.
Keywords: acetylenic alcohols, dibenzo-18-crown-6, diazotization.
Acetylenic alcohols are of considerable interest Acetylene alcohols are widespread in various due to a wide range of their useful properties; in ad- natural resources: in plants, fungi, bacteria, algae, dition, these compounds serve as objects for the study and in sponges [1, 399-402]; possess several re-ofmany fundamental problems oforganic chemistry. action centers [2, 1924-1928], have an OH- and
Acetylene compounds play an important role as acetylene group, are potential donors of hydrogen unique synthons with high synthetic potential, since bonds, as well as acceptors [3, 54318-54325], ex-the triple bond is prone to electrophilic, radical, and hibit anticorrosive properties [4, 496-508]. Acety-bipolar addition reactions, as well as transformation lene lipids have been created to determine the con-involving the methine hydrogen atom with abnor- figurations of aminoalkanes [5, 2291-2298] and mally high acidity. many others [6, 101-112].
H,N
+
N=N
2Cl-
C—C—C—R2
I: R1=R2 = -C H3; II: R = - CH3, R2= -C2H5; III: R = -H, R2= -C2H5
There are many ways to introduce the C=C fragment into an organic molecule [7, 23-25]. Many works on the synthesis of acetylene compounds of benzocrown ethers are based on the Heck-Sono-gashira reaction [8, 27-39], cross-coupling of terminal alkynes with aryl halides. Earlier [9, 18-21], we obtained tertiary acetylenic alcohols diben-zo-18-crown-6 by the Favorsky method, but the ethynyl group - C = C - is linked to the aromatic system through 1 carbon atom.
The main goal of this study is the synthesis of tertiary acetylene alcohol by diazotization of 4', 4"-diaminodibenzo-18-crown-6 and subsequent reaction with acetylenic alcohols with the evolution of nitrogen. A feature of this synthesis is the forma-
tion of a product with a C=C triple bond directly linked to the benzene ring of dibenzo-18-crown-6.
Acetylenic alcohols dibenzo-18-crown-6 were synthesized by the diazotization method 4',4''-di-aminodibenzo-18-crown-6. The resulting salt of the diazo compound dibenzo-18-crown-6 is formed by the interaction of the diamino derivative of dibenzo-18-crown-6 with sodium nitrite in dilute hydrochloric acid in the presence of copper (I) salts. Diazonium salt based on 4',4' '-diaminod-ibenzo-18-crown-6 is stable during the day, when interacting with acetylenic alcohols with a terminal triple bond, acetylenic alcohols dibenzo-18-crown-6 are formed, in the molecule of which there is a triple bond directly at the benzene nucleus of the macro-
cycle.
Table 1. - Some characteristics of a series of 4', 4"-diacetylenic alcohols based on 4', 4''-diaminodibenzo-18-crown-6
№ Compounds m.p. C Yeild,% Found,% Gross formula Calculated,%
C H C H O
I 4',4"-di-(3-methyl-3-ol-butynyl) -DB18C6 178-182 28 68.38 6.82 C30H36O8 68.70 6.87 24.43
II 4',4"-di- (3-methyl-3-ol-pentynyl) -DB18C6 194-198 26 70.04 7.37 C32H40O8 69.57 7.24 23.19
III 4',4"-di- (3-ol-pentynyl) -DB18C6 206-211 32 68.97 6.94 C30H36O8 68.70 6.87 24.43
The obtained elemental analysis data are in agreement with the calculated data. The increase in the melting point of the homologous series of acetylenic alcohols, dibenzo-18-crown-6, is similar to the homologous series of alkynes.
13C spectra show new signals characteristic of the C-C bond of quaternary substituted carbon, acetylenic carbons and individual signals of radicals.
The diazotization process was carried out at a temperature of 0-50C, the rationale for this is that with increasing temperature, the formation of byproducts increases. The process was carried out for 2 hours while stirring the reaction mixture. The structures of the obtained compounds were proved by modern physicochemical methods (table 1,2,3).
Experimental part
and 13C-NMR spectra were obtained in a CDCl3 solution on a Bruker VXR-400 spectrometer at an operating frequency of400 MHz, using a TMS solvent as an internal standard (7.27 ppm by TMS)
Melting points were determined in the usual way in a metal block.
4', 4''-diaminodibenzo-18-crown-6 was obtained according to [10, 878-884]. Yield 5.0g (72%) mp. 176-178 °C. Lit. data. [10, 878-884] m.p. 177178 °C.
4',4''-dibenzo-18-crown-6-yl-diazonium chloride was obtained from 2.5 g (6.41 mmol) of 4',4"-diaminodibenzo-18-crown-6, 83 ml of water with 3 ml (32.96 mmol) of 34% HCl. Then the so-
Table 2. - Data of 1H-NMR spectra of 4', 4"-diacetylenic alcohols based on 4', 4"-diaminodibenzo-18-crown-6 (8, ppm)
№ Compounds Individual a-CH3 -OH p-o-CH2 a-OCH2 Ar-CH 6',6" Ar-CH 3',3" Ar-CH 5 ,5"
1 2 3 4 5 6 7 8 9 10
I 4',4"-di-(3-methyl-3-ol-butynyl) -DB18C6 1.48 (12H, s) 2.96 (2H, s) 3.89-4.02 (8H, m) 4.24-4.26 (8H, m) 6.69 (2H,s) 6.81 (2H, m) 6.83 (2H, m)
II 4',4"-di-(3-methyl-3-ol-pentynyl) -DB18C6 1.16 (6H, s, R-CH3) 1.65-1.67 (4H,S,CH2) 1.36 (6H,s) 2.86 (2H,s) 3.87-3.94 (8H, m) 4.12-4.22 (8H, m) 6.67 (2H,s) 6.73 (2H, d) 6.78-6.80 (2H, d)
III 4',4"-di-(3-ol-penty-nyl)-DB18C6 1.94 (4H, d)R-CH2 4.60-4.62 (2H, s,-CH-OH) 1.10 (6H,s) 2.75 (2H, s) 3.81-3.92 (8H, m) 4.07-4.18 (8H, m) 6.68 (2H,s) 6.72 (2H, d) 6.76-6.80 (2H, d)
Table 3. - Data of 13C-NMR spectra of 4', 4"-diacetylenic alcohols based on 4', 4"-diaminodibenzo-18-crown-6 (8, ppm)
Compounds Individual -CH3 (2C) 1 —c— 1 (2C) p-o-CH2 a-0-CH2 (8C) -C=CR(2C) -C=CR(2C) Ar-CH 3',3" (2C) Ar-CH 6,6" (2C) Ar-CH 5',5" (2C) Ar-C-4,4" (2C) Ar-C- 2',2" (2C) Ar-C-l',l" (4C)
I 4',4"-di-(3-methyl-3-ol-bu-tynyl) -DB18C6 31.35 (4C) 65.83 69.64 70.49-71.08 81.19 93.10 117.38 114.16 124.36 116.52 149.54 150.49
II 4',4"-di-(3-methyl-3-ol-pen-tynyl) -DB18C6 9.00 (2C, R-CH3) 36.26 (2C, -CH2-) 28.29 68.75 69.58 70.32-71.04 80.82 93.19 117.19 113.25 124.17 116.42 149.52 150.41
III 4',4"-di-(3-ol-pentynyl)-DB18C6 9.90 (2C, R-CH3) 30.80 (2C, -CH2-) 64.40 CH-OH 68.97 70.02-70.94 86.25 96.43 117.53 112.97 124.51 116.54 149.54 150.57
lution was cooled in an ice bath to 00C and 0.92 g (13.33 mmol) NaNO2 was added. The resulting dia-zonium salt was not isolated. For each reaction, the diazonium salt of dibenzo- 18-crown-6 was prepared separately according to equimolecular ratios.
4',4"-di-(3-methyl-3-ol-butynyl)-diben-zo-18-crown-6 (I). To a freshly prepared equimolar ratio of 4', 4''-dibenzo-18-crown-6-yldiazonium chloride 2.5 g (6.41 mmol) with mechanical stirring in an ice bath was added 3-methylbutin- 1-ol-3 6.84 ml (7.692 mmol, d = 1.0595 g/cm3), gas evolution was observed. The progress of the reaction was monitored by TLC on silufol, in the system acetone: hexane 2:1. The reaction time was 2 hours. It was purified by column chromatography, eluent hexane. Light yellow powder, m.p. 178-182 °C. Yield 0.94g, (28%).
1H NMR (CDCl3, 400 MHz) SH, m.p.: 1.48 (12H, s, -CH3), 2.96 (2H, s, -OH), 3.89-4.26 (16H, d. m, a-, p-O-CHj), 6.69 (2H, d, Ar-H 3'), 6.81 (2H, d, Ar-H 6'), 6.83 (2H, d, Ar-H 5'). 13C NMR (CDCl3, 100 MHz) S, m.p.: 31.35(4C, -CH3), 65.83 (2C3, -C-), 69.64-71.08 (8C, p-a-O-CH2), 81.19 (2C, ArC=), 93.10 (2C, ArC=C-), 114.16 (2C, Ar-C 6'), 117.38-124.36 (6C, Ar-C 3',5',6'), 150.49 (4C, Ar C4'). Elemental analysis: Found,%: C 68.38, H 6.82. Calculated,%: C 68.70, H 6.87, O 24.43, Gross formula: C30H36O8.
4',4"-di-(3-methyl-3-ol-pentynyl) -diben-zo-18-crown-6 (II). By analogy with (I) 2.5 g (6.41 mmol) 4',4''-dibenzo-18-crown-6-yldiazonium chloride, 3-methylpentin-1-ol-3 6.23 ml (7.692
mmol, d = 1.061 g/cm3). m.p. 194-1980C, yield 0.92 g (26%). 1H NMR (CDCl3, 400 MHz) SH, m.p.: 1.16 (6H, s, R-CH3) 1.36 (6H, s, -CH3), 1.65-1.67 (4H, s, -CH2), 2.86 (2H, s, -OH), 3.87-4.22 (16H, d. m, a-, ß-O-CH2), 6.67 (2H, d, Ar-H 3'), 6.73 (2H, d, Ar-H 6'), 6.78-6.80 (2H, d, Ar-H 5'). 13C NMR (CDCl3, 100 MHz) S, m.p.: 9.00 (2C, R-CH3), 28.29(2C, -CH3), 36.26 (2C,-CH2 -), 68.75 (2C, -C-), 69.58-71.04 (8C, ß-a-O-CH2), 80.82 (2C, ArC=), 93.19 (2C, ArC=C-), 113.25 (2C, Ar-C 4'), 116.42-124.17 (6C, Ar-C 3',5',6'), 150.41 (4C, ArC4'). Elemental analysis: Found,%: C 70.04, H 7.37. Calculated,%: C 69.57, H 7.24, O 23.19, Gross
formula: C32H4008.
4', 4''-di- (3-ol-pentynyl) -diben-zo-18-crown-6 (III). By analogy with (I) 2.5 g (6.41 mmol) 4',4''-dibenzo-18-crown-6-yldiazo-nium chloride, pentin-1-ol-3 6.21 ml (7.692 mmol, d =1.0598 g/cm3). m.p. 206-2110C, yield 1.075 g (32%). 1H NMR (CDCl3, 400 MHz) SH, m.p.: 1.10 (6H, s, -CH3), 1.94 (4H, d, -R-CH2), 2.75 (2H, s, -OH), 3.81-4.18 (16H, d. m, a-, ß-O-CH2), 4.604.62 (2H, s, -CH-OH), 6.68 (2H, d, Ar-H 3'), 6.72 (2H, d, Ar-H 6'), 6.76-6.80 (2H, d, Ar-H 5'). 13C NMR (CDCl3, 100 MHz) S, m.p.: 9.90 (2C, -CH3), 30.80 (2C, -CH2), 64.40 (2C, -CH-OH), 68.9770.94 (8C, ß-a-O-CH2), 86.25 (2C, ArC=), 96.43 (2C, ArC=C-), 112.97 (2C, Ar-C 4'), 116.54124.51 (6C, Ar-C 3',5',6'), 150.57 (4C, ArC4'). Elemental analysis: Found,%: C 68.97, H 6.94. Cal-culated,%: C 68.70, H 6.87, O 24.43, Gross formula:
C30H36O8.
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