CN101941949A - Triazole heterocyclic compound and synthesis method thereof - Google Patents
Triazole heterocyclic compound and synthesis method thereof Download PDFInfo
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- CN101941949A CN101941949A CN 201010278977 CN201010278977A CN101941949A CN 101941949 A CN101941949 A CN 101941949A CN 201010278977 CN201010278977 CN 201010278977 CN 201010278977 A CN201010278977 A CN 201010278977A CN 101941949 A CN101941949 A CN 101941949A
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Abstract
The invention relates to a triazole heterocyclic compound and a synthesis method thereof, belonging to the technical field of organic synthesis of liquid crystal compounds and liquid crystal materials. The triazole heterocyclic compound is synthetized from azido benzoate and acetenyl benzoate by a click chemistry method. The nolinear triazole heterocyclic compound synthetized by a simple, convenient and easily operated method has the advantages of wider SmA phase, good stability and the like; and in addition, the triazole heterocyclic compound also has the obvious advantages of aromaticity, large dipole moment and the like, and can change the dipole moment, the dielectric anisotropy, luminescence and other performances of liquid crystal molecular, thus introduction of the triazole heterocyclic compound into the liquid crystal molecular has great significance for researching the liquid crystal performance of the compound, designing and developing novel function materials, etc.
Description
Technical field
The present invention relates to a class and contain triazole heterogeneous ring compound and synthetic method thereof, belong to the technical field of organic synthesis of liquid crystalline cpd and liquid crystal material.
Background technology
In recent years, liquid crystalline cpd and liquid crystal material have obtained using widely in each side such as electronics, optics, acoustics, biotechnology, chemical industry, become one of focus of applied chemistry and materials chemistry research.Therefore the novel liquid crystal material is synthetic, and the structure of liquid crystal molecule and the relation between the performance become an integral part of research.
The factor of decision liquid crystal practical application mainly contains the symbol and size, optical anisotropy etc. of mesomorphic phase kind, phase transition temperature, dielectric anisotropy, and the heterocycle liquid crystal these play an important role in nature in raising.
The heteroatomic introducing that polarizability is big can influence the polarity of molecule, other heteroatoms may influence molecular interaction thereby geometric configuration influences the phase transition temperature of liquid crystal, make mesomorphic phase type (the Parra M L of liquid crystal molecule, Saavedra C G, Hidalgo P I.Liquid Crystals, 2008,35 (1): 55-64.), dipole moment direction and size, and the symbol of dielectric anisotropy and size (Dingemans T J, Murthy N S, Samulski E T.J.Phys.Chem.B, 2001,105:8845-8860.) etc. change, also may influence the luminous of molecule and other character in addition.Thereby contain the heterocyclic liquid crystal the design synthesizing new functional materials aspect playing an important role.
Contain the compound of [1,2,3]-triazole ring because it has plurality of advantages such as chemical stability height, dipole moment are big, aromaticity, be widely used in every field such as materials chemistry, organic chemistry, pharmaceutical chemistry and biological chemistry.Can be used as dyestuff, sanitas, photostabilizer and photoelectric material etc., and triazole ring is less relatively as the research of liquid crystal material.
Summary of the invention
The purpose of this invention is to provide a class and contain triazole heterogeneous ring compound and synthetic method thereof, should adopt easy, easy-operating method to synthesize non-linear triazole heterogeneous ring compound, this compound should have characteristics such as the SmA phase, good stability of broad; Also should have outstanding advantages such as aromaticity, dipole moment be big, can change the dipole moment, dielectric anisotropy of liquid crystal molecule, various character such as luminous.
Technical scheme of the present invention is: the molecular structural formula that a class contains the triazole heterogeneous ring compound is:
R wherein
1For: the straight chained alkyl of 2-12 carbon atom, branched-chain alkyl or chirality alkyl;
R wherein
2For: the straight chain ester group of 2-12 carbon atom, side chain ester group, chirality ester group, straight chain alkoxyl group, branched alkoxy, chirality alkoxyl group,
A described class contains the synthetic method of triazole heterogeneous ring compound by synthesizing through the click chemistry method to the triazobenzene manthanoate and to the acetylenylbenzene manthanoate, and its synthesis step is as follows:
(1) be raw material with para-amino benzoic acid and dehydrated alcohol, the vitriol oil is made catalyzer, makes parathesin;
(2) under the ice-water bath condition, in molar ratio 1 part of parathesin is dissolved in 1 part of concentrated hydrochloric acid and the 1 part of water, add 2 parts of Sodium Nitrites after 10-30 minute, be incubated 0～5 ℃ 1-2 hour, slowly add 2 parts of sodiumazide, stopped reaction after 10-45 minute, filtration, washing, dry must be to the triazobenzene manthanoate;
(3) be that raw material prepares the parabromobenzoic acid ethyl ester through esterification with the parabromobenzoic acid;
(4) in molar ratio, with 10 parts of parabromobenzoic acid ethyl esters, 12 parts of 2-methyl-3-butyne-2-alcohols, 0.1 part of triphenylphosphine, 0.05 part of cuprous iodide, 0.01 part of bi triphenyl phosphine dichloride palladium and 15 parts of anhydrous triethylamines and 5 parts of pyridines, under nitrogen protection back flow reaction 1-3 hour, pour in the water, extract, cross the post separation and obtain 4-(3-hydroxy-3-methyl-1-propine) ethyl benzoate;
(5) in molar ratio, the adding of 10 parts of 4-(3-hydroxy-3-methyl-1-propine) ethyl benzoate is dissolved with in the Virahol of 40 parts of potassium hydroxide, backflow 1-5 hour, filtered while hot got the benzoic sylvite of 4-ethynyl;
(6) in molar ratio, 2 parts of benzoic sylvite of 4-ethynyl are suspended in 5-20 part chloroform, add 4-10 part sulfur oxychloride under the ice-water bath condition, steamed solvent in room temperature reaction 4-10 hour, add 2 parts of corresponding alcohol, methylene dichloride is made solvent, and refluxing under anhydrous pyridine catalysis makes 4-acetylenylbenzene manthanoate;
(7) with described to the triazobenzene manthanoate with the acetylenylbenzene manthanoate is made target product through the click chemistry method, mol ratios such as employing to triazobenzene manthanoate and 4-acetylenylbenzene manthanoate in the presence of 1 equivalent cupric sulfate pentahydrate and 3 normal sodium ascorbates, with the tetrahydrofuran (THF) and the water as solvent of equal-volume ratio, can obtain containing the triazole heterogeneous ring compound in room temperature reaction 8-72 hour.
Concrete synthetic route is as follows:
Synthetic route 1:
Promptly generate parathesin (II) through esterification, (II) generate triazobenzene ethyl formate (A) with reaction of sodium azide after the diazotization with para-amino benzoic acid (I).Parabromobenzoic acid (III) is a starting raw material, generates parabromobenzoic acid ethyl ester (IV) through esterification; Compound (IV) makes 4-(3-hydroxy-3-methyl-butyl) ethyl benzoate (V) with 2-methyl-3-butyl-2-alcohol through the Sonogashira linked reaction; Compound (V) takes off acetone and obtains the benzoic sylvite of alkynyl (VI) under strong alkaline condition; Compound (VI) generates corresponding ester (B with sulfur oxychloride reaction becoming acyl chlorides (VII), last (VII) with the alcohol reaction
n).(A) and (B
n) by the synthetic end product (T of click chemistry reaction
1 n).
Synthetic route 2:
Be starting raw material promptly, generate butoxy oil of mirbane (b) through etherificate with p-NP (a); Compound (b) is through SnCl
22H
2The O reduction obtains butoxy aniline (c); Generate butoxy phenylazide (C) with reaction of sodium azide after compound (c) diazotization.(C) and (B
n) by the synthetic end product (T of click chemistry reaction
2 n).
Synthetic route 3:
Promptly to be starting raw material to hexyloxybenzoate (i), nitrophenyl-4-hexyloxybenzoate ester (ii) to generate 4-through esterification; Compound is (ii) through SnCl
22H
2O reduction obtains that the 4-aminophenyl-4-hexyloxybenzoate ester (iii); Compound (iii) generates 4-azido-phenyl-4-hexyloxybenzoate ester (D) with reaction of sodium azide after the diazotization.(D) and (B
5) by the synthetic end product (T of click chemistry reaction
3).
Synthetic route 4:
Be starting raw material promptly, generate 1,4-two phenylazides (E) with reaction of sodium azide after the diazotization with Ursol D (1).(E) and (B
5) by the synthetic end product (T of click chemistry reaction
4).
This compounds is measured with POM through DSC has SmA mutually.
Beneficial effect of the present invention: this class contains the triazole heterogeneous ring compound by synthesizing through the click chemistry method to the triazobenzene manthanoate and to the acetylenylbenzene manthanoate.Adopt the non-linear triazole heterogeneous ring compound of easy, easy-operating method synthetic to have the characteristics such as SmA phase, good stability of broad.Contain triazole heterocyclic compound in addition and also have outstanding advantages such as aromaticity, dipole moment be big, can change the dipole moment, dielectric anisotropy of liquid crystal molecule, various character such as luminous, thereby in the liquid crystal molecule that the triazole heterogeneous ring compound is introduced, study this compounds liquid crystal property, to design and develop new-type functional material etc. significant.
Embodiment
Below with R
1The n-hexyl that is 6 carbon atoms is an example, and four kinds of synthetic methods that contain triazole heterocycle liquid crystalline cpd are described.
The structural formula of four kinds of compounds is as follows:
Embodiment 1: preparation R
1N-hexyl, R
2For
Compound (T
1 5)
(1), the preparation of 4-triazobenzene ethyl formate (A):
Add 0.685g (5mmol) para-amino benzoic acid, 5mL ethanol in the 10mL single port bottle, the catalytic amount vitriol oil, temperature rising reflux 3h.Cooling is poured in the water, uses saturated Na
2CO
3Be neutralized to pH=7-8, filtration washing, the dry 0.284g white p-subcutin solid (II) that gets.Productive rate: 42.0%, M.p:18.9-19.3 ℃.
Add 165mg (1mmol) p-subcutin (II) in the 10mL single port bottle, dense HCl of 1.5mL and 1.5mL water, ice-water bath adds water-soluble 104mgNaNO
2, stir 1h, add the 100mgNaN of molten water again
3, stir 30min.Filter, natural drying at room temperature gets light yellow solid (A) 70mg.Productive rate: 73.3%, M.p:95.5-97.0 ℃.
Same method can make following compound:
4-triazobenzene propyl formate
4-triazobenzene butyl formate
4-triazobenzene pentyl formate
4-triazobenzene hexyl formate
4-triazobenzene heptyl formate
4-triazobenzene octyl formate
4-triazobenzene nonyl formate
4-azido-n-decyl benzoate
(2), 4-acetylenylbenzene hexyl formate (B
5) preparation:
Add 1.005g (5mmol) parabromobenzoic acid, 10mL ethanol and the catalytic amount vitriol oil in the 25mL single port bottle, backflow 2h.Reaction solution is poured in the frozen water CH into after being cooled to room temperature
2Cl
2(2 * 50mL) extracted organic phase are used 5%NaHCO respectively
3Solution (2 * 30mL), (2 * 50mL) washing organic phases, anhydrous magnesium sulfate drying filters saturated NaCl solution, screws out solvent and gets yellow parabromobenzoic acid ethyl ester (IV) liquid, productive rate 92.8%.
Add 8mg bi triphenyl phosphorus palladium chloride in the 25mL two-mouth bottle, 3mg CuI, 0.645g (3mmol) parabromobenzoic acid ethyl ester, 3mmol 2-methyl-3-butyl-2-alcohol, 4mL triethylamine and 1.5mL pyridine, N
2Protection is backflow 1h down.Reaction solution is cooled to room temperature, pours in the water CH into
2Cl
2Extracted organic phase, anhydrous magnesium sulfate drying was spin-dried for post and got light yellow solid (V), productive rate 85.0%.
Add 0.581g alkynes ester (V), 0.560g KOH, 12mL Virahol in the 25mL single port bottle, backflow 1h cooling is filtered, and the washed with isopropyl alcohol of heat gets white solid (VI), productive rate 85.0% twice.
Add 368mg (VI) in the 25mL single port bottle, 1.5mL SOCl
2, 10mL CHCl
3, room temperature reaction 6h steams solvent, gets compound (VII), does not handle and directly does next step reaction.In former reaction flask, add 400 μ L n-hexyl alcohols, 10mL CHCl
3, 0.5mL pyridine back flow reaction 2h steams solvent, cross post separate light yellow solid (B
5) 377mg, two step productive rates 81.8%.
Use the same method and to make following compound
4-acetylenylbenzene ethyl formate
4-acetylenylbenzene propyl formate
4-acetylenylbenzene butyl formate
4-acetylenylbenzene pentyl formate
4-acetylenylbenzene heptyl formate
4-acetylenylbenzene octyl formate
4-acetylenylbenzene nonyl formate
4-ethynyl n-decyl benzoate
(3), the own oxygen carbonyl-1H-[1 of 4-ethoxycarbonyl-4`-, 2,3]-triazole
Add 191mg (1mmol) 4-triazobenzene ethyl formate in the 25mL single port bottle, 4-acetylenylbenzene hexyl formate and THF/H
2O (5mL: 3mL).Stir and add 125mg cupric sulfate pentahydrate that is dissolved in the 1mL water and the 300mg sodium ascorbate that is dissolved in the 1mL water down, room temperature lucifuge stirring 3d.Pour into and get brown solid in the water, suction filtration, washing, sherwood oil flushing solid, dry light solid 224mg, the productive rate 53.14% of getting.
1H NMR (CDCl
3, 400MHz): δ (ppm): 8.352 (s, 1H, Triazole ring C-
H), 8.253 (d, J=8.8Hz, 2H), 8.151 (d, J=8.4Hz, 2H), 8.006 (d, J=8.4Hz, 2H), 7.918 (d, J=8.8Hz, 2H), J
1=8Hz, J
2=4Hz, 2H), 4.41-4.46 (m, 2H), 1.76-1.83 (m, 2H), 1.30-1.35 (m, 3H), 1.42-1.48 (m, 6H), 0.87-0.91 (m, 3H), TOF MS EI+: experimental value: 421.2290, theoretical value: 421.2002.
Same method can make following compound:
4-ethoxycarbonyl-4`-ethoxycarbonyl-1H-[1,2,3]-triazole
4-ethoxycarbonyl-4`-third oxygen carbonyl-1H-[1,2,3]-triazole
4-ethoxycarbonyl-4`-butoxy carbonyl-1H-[1,2,3]-triazole
4-ethoxycarbonyl-4`-penta oxygen carbonyl-1H-[1,2,3]-triazole
4-ethoxycarbonyl-4`-oxygen in heptan carbonyl-1H-[1,2,3]-triazole
The hot oxygen carbonyl-1H-[1 of 4-ethoxycarbonyl-4`-, 2,3]-triazole
4-ethoxycarbonyl-4`-oxygen in ninth of the ten Heavenly Stems carbonyl-1H-[1,2,3]-triazole
4-ethoxycarbonyl-4`-oxygen in last of the ten Heavenly stems carbonyl-1H-[1,2,3]-triazole
4-third oxygen carbonyl-4`-ethoxycarbonyl-1H-[1,2,3]-triazole
4-third oxygen carbonyl-4`-third oxygen carbonyl-1H-[1,2,3]-triazole
4-third oxygen carbonyl-4`-butoxy carbonyl-1H-[1,2,3]-triazole
4-third oxygen carbonyl-4`-penta oxygen carbonyl-1H-[1,2,3]-triazole
The own oxygen carbonyl-1H-[1 of 4-third oxygen carbonyl-4`-, 2,3]-triazole
4-third oxygen carbonyl-4`-oxygen in heptan carbonyl-1H-[1,2,3]-triazole
The hot oxygen carbonyl-1H-[1 of 4-third oxygen carbonyl-4`-, 2,3]-triazole
4-third oxygen carbonyl-4`-oxygen in ninth of the ten Heavenly Stems carbonyl-1H-[1,2,3]-triazole
4-third oxygen carbonyl-4`-oxygen in last of the ten Heavenly stems carbonyl-1H-[1,2,3]-triazole
4-butoxy carbonyl-4`-ethoxycarbonyl-1H-[1,2,3]-triazole
4-butoxy carbonyl-4`-third oxygen carbonyl-1H-[1,2,3]-triazole
4-butoxy carbonyl-4`-butoxy carbonyl-1H-[1,2,3]-triazole
4-butoxy carbonyl-4`-penta oxygen carbonyl-1H-[1,2,3]-triazole
The own oxygen carbonyl-1H-[1 of 4-butoxy carbonyl-4`-, 2,3]-triazole
4-butoxy carbonyl-4`-oxygen in heptan carbonyl-1H-[1,2,3]-triazole
The hot oxygen carbonyl-1H-[1 of 4-butoxy carbonyl-4`-, 2,3]-triazole
4-butoxy carbonyl-4`-oxygen in ninth of the ten Heavenly Stems carbonyl-1H-[1,2,3]-triazole
4-butoxy carbonyl-4`-oxygen in last of the ten Heavenly stems carbonyl-1H-[1,2,3]-triazole
4-penta oxygen carbonyl-4`-ethoxycarbonyl-1H-[1,2,3]-triazole
4-penta oxygen carbonyl-4`-third oxygen carbonyl-1H-[1,2,3]-triazole
4-penta oxygen carbonyl-4`-butoxy carbonyl-1H-[1,2,3]-triazole
4-penta oxygen carbonyl-4`-penta oxygen carbonyl-1H-[1,2,3]-triazole
The own oxygen carbonyl-1H-[1 of 4-penta oxygen carbonyl-4`-, 2,3]-triazole
4-penta oxygen carbonyl-4`-oxygen in heptan carbonyl-1H-[1,2,3]-triazole
The hot oxygen carbonyl-1H-[1 of 4-penta oxygen carbonyl-4`-, 2,3]-triazole
4-penta oxygen carbonyl-4`-oxygen in ninth of the ten Heavenly Stems carbonyl-1H-[1,2,3]-triazole
4-penta oxygen carbonyl-4`-oxygen in last of the ten Heavenly stems carbonyl-1H-[1,2,3]-triazole
The own oxygen carbonyl of 4--4`-ethoxycarbonyl-1H-[1,2,3]-triazole
The own oxygen carbonyl-4`-third oxygen carbonyl-1H-[1 of 4-, 2,3]-triazole
The own oxygen carbonyl of 4--4`-butoxy carbonyl-1H-[1,2,3]-triazole
The own oxygen carbonyl-4`-penta oxygen carbonyl-1H-[1 of 4-, 2,3]-triazole
The own oxygen carbonyl-1H-[1 of the own oxygen carbonyl-4`-of 4-, 2,3]-triazole
The own oxygen carbonyl of 4--4`-oxygen in heptan carbonyl-1H-[1,2,3]-triazole
The hot oxygen carbonyl-1H-[1 of the own oxygen carbonyl of 4--4`-, 2,3]-triazole
The own oxygen carbonyl of 4--4`-oxygen in ninth of the ten Heavenly Stems carbonyl-1H-[1,2,3]-triazole
The own oxygen carbonyl of 4--4`-oxygen in last of the ten Heavenly stems carbonyl-1H-[1,2,3]-triazole
4-oxygen in heptan carbonyl-4`-ethoxycarbonyl-1H-[1,2,3]-triazole
4-oxygen in heptan carbonyl-4`-third oxygen carbonyl-1H-[1,2,3]-triazole
4-oxygen in heptan carbonyl-4`-butoxy carbonyl-1H-[1,2,3]-triazole
4-oxygen in heptan carbonyl-4`-penta oxygen carbonyl-1H-[1,2,3]-triazole
The own oxygen carbonyl-1H-[1 of 4-oxygen in heptan carbonyl-4`-, 2,3]-triazole
4-oxygen in heptan carbonyl-4`-oxygen in heptan carbonyl-1H-[1,2,3]-triazole
The hot oxygen carbonyl-1H-[1 of 4-oxygen in heptan carbonyl-4`-, 2,3]-triazole
4-oxygen in heptan carbonyl-4`-oxygen in ninth of the ten Heavenly Stems carbonyl-1H-[1,2,3]-triazole
4-oxygen in heptan carbonyl-4`-oxygen in last of the ten Heavenly stems carbonyl-1H-[1,2,3]-triazole
The hot oxygen carbonyl of 4--4`-ethoxycarbonyl-1H-[1,2,3]-triazole
The hot oxygen carbonyl-4`-of 4-third oxygen carbonyl-1H-[1,2,3]-triazole
The hot oxygen carbonyl of 4--4`-butoxy carbonyl-1H-[1,2,3]-triazole
The hot oxygen carbonyl-4`-of 4-penta oxygen carbonyl-1H-[1,2,3]-triazole
The own oxygen carbonyl-1H-[1 of the hot oxygen carbonyl-4`-of 4-, 2,3]-triazole
The hot oxygen carbonyl of 4--4`-oxygen in heptan carbonyl-1H-[1,2,3]-triazole
The hot oxygen carbonyl of the 4--hot oxygen carbonyl-1H-[1 of 4`-, 2,3]-triazole
The hot oxygen carbonyl of 4--4`-oxygen in ninth of the ten Heavenly Stems carbonyl-1H-[1,2,3]-triazole
The hot oxygen carbonyl of 4--4`-oxygen in last of the ten Heavenly stems carbonyl-1H-[1,2,3]-triazole
4-oxygen in ninth of the ten Heavenly Stems carbonyl-4`-ethoxycarbonyl-1H-[1,2,3]-triazole
4-oxygen in ninth of the ten Heavenly Stems carbonyl-4`-third oxygen carbonyl-1H-[1,2,3]-triazole
4-oxygen in ninth of the ten Heavenly Stems carbonyl-4`-butoxy carbonyl-1H-[1,2,3]-triazole
4-oxygen in ninth of the ten Heavenly Stems carbonyl-4`-penta oxygen carbonyl-1H-[1,2,3]-triazole
The own oxygen carbonyl-1H-[1 of 4-oxygen in ninth of the ten Heavenly Stems carbonyl-4`-, 2,3]-triazole
4-oxygen in ninth of the ten Heavenly Stems carbonyl-4`-oxygen in heptan carbonyl-1H-[1,2,3]-triazole
The hot oxygen carbonyl-1H-[1 of 4-oxygen in ninth of the ten Heavenly Stems carbonyl-4`-, 2,3]-triazole
4-oxygen in ninth of the ten Heavenly Stems carbonyl-4`-oxygen in ninth of the ten Heavenly Stems carbonyl-1H-[1,2,3]-triazole
4-oxygen in ninth of the ten Heavenly Stems carbonyl-4`-oxygen in last of the ten Heavenly stems carbonyl-1H-[1,2,3]-triazole
4-oxygen in last of the ten Heavenly stems carbonyl-4`-ethoxycarbonyl-1H-[1,2,3]-triazole
4-oxygen in last of the ten Heavenly stems carbonyl-4`-third oxygen carbonyl-1H-[1,2,3]-triazole
4-oxygen in last of the ten Heavenly stems carbonyl-4`-butoxy carbonyl-1H-[1,2,3]-triazole
4-oxygen in last of the ten Heavenly stems carbonyl-4`-penta oxygen carbonyl-1H-[1,2,3]-triazole
The own oxygen carbonyl-1H-[1 of 4-oxygen in last of the ten Heavenly stems carbonyl-4`-, 2,3]-triazole
4-oxygen in last of the ten Heavenly stems carbonyl-4`-oxygen in heptan carbonyl-1H-[1,2,3]-triazole
The hot oxygen carbonyl-1H-[1 of 4-oxygen in last of the ten Heavenly stems carbonyl-4`-, 2,3]-triazole
4-oxygen in last of the ten Heavenly stems carbonyl-4`-oxygen in ninth of the ten Heavenly Stems carbonyl-1H-[1,2,3]-triazole
4-oxygen in last of the ten Heavenly stems carbonyl-4`-oxygen in last of the ten Heavenly stems carbonyl-1H-[1,2,3]-triazole
Embodiment 2: preparation R
1Be n-hexyl, R
2For
Compound (T
2 5)
(1) preparation of 4-butoxy aniline
In being housed, the 25mL bottle with two necks of spherical reflux condensing tube and constant pressure funnel adds 278mg (2mmol) p-NP (a), 828mg (6mmol) K
2CO
3, 23mg KI, 10mL acetone adds the 302mg bromination of n-butane in the constant pressure funnel.Be warming up to backflow, slowly drip bromination of n-butane, back flow reaction 24h, the some plate reacts completely.Suction filtration, the washing with acetone filter cake, be spin-dried for tawny 4-butoxy oil of mirbane (b) liquid.
Add 1.44mmol 4-butoxy oil of mirbane (b), 1.5g SnCl in the 25mL single port bottle
22H
2O, 10mL ethanol, back flow reaction 24h, the some plate reacts completely.Pour in the water with 1N NaOH solution and transfer pH to neutral, extracted with diethyl ether, organic phase are used saturated aqueous common salt, water washing successively, and anhydrous magnesium sulfate drying screws out solvent and gets sorrel liquid, cross post separate 174mg sorrel 4-butoxy aniline (c) liquid.
(2) preparation of 4-butoxy phenylazide
Add 174mg 4-butoxy aniline (c), 3mL concentrated hydrochloric acid and 3mL water, ice-water bath 30min in the 25mL single port bottle.Add water-soluble 110mg NaNO
2, ice-water bath slowly drips water-soluble 102mgNaN after stirring 1h
3, ice-water bath stirs 30min, CH
2Cl
2Extraction, anhydrous magnesium sulfate drying screws out solvent and gets sorrel 4-butoxy phenylazide (C) liquid.
(3) preparation of 4-acetylenylbenzene hexyl formate is with embodiment 1
(4) 4-(1-(4-butoxy) phenyl)-1H-[1,2,3]-triazol radical hexyl-benzoate (T
2 5) preparation with embodiment 1
1HNMR(CDCl
3，400MHz)：δ(ppm)：8.191(s，1H，triazole?ring?C-H)，8.138(d，J＝8.4Hz，2H)，7.987(d，J＝8.4Hz，2H)，7.674(d，J＝8.8Hz，2H)，7.055(d，J＝8.8Hz，2H)，4.354(t，J＝6.4Hz，2H)，4.038(t，J＝6.4Hz，2H)，1.747-1.853(m，4H)，1.476-1.546(m，8H)，1.003(t，J＝7.4Hz，6H).
TOF MS EI+: experimental value: 421.2372, theoretical value: 421.2365.
Embodiment 3: preparation R
1Be n-hexyl, R
2For
Compound (T
3)
(1) preparation of 4-nitrophenyl-4-hexyloxy benzene methyl
In being housed, the 25mL single port bottle of tail gas collecting device adds 444mg (2mmol) to hexyloxybenzoate (i), 5mL SOCl
2, back flow reaction 4-5h, decompression steams SOCl
2Add the 278mg p-NP, 0.5mL pyridine, 5mL CH
2Cl
2Back flow reaction 3h steams solvent, washing, CH
2Cl
2Extraction, anhydrous magnesium sulfate drying screws out solvent and gets (ii) solid 666mg of oyster white 4-nitrophenyl-4-hexyloxy benzene methyl, productive rate 96%.
(2) preparation of 4-aminophenyl-4-hexyloxy benzene methyl
In 10mL single port bottle, add 174mg (0.5mmol) 4-nitrophenyl-4-hexyloxy benzene methyl (ii), 0.55g SnCl
22H
2O, 3mL ethanol, back flow reaction 3h, the some plate reacts completely.Pour in the water and transfer pH=7, get (iii) solid of white 4-aminophenyl-4-hexyloxy benzene methyl, suction filtration vacuum-drying with 10%NaOH solution.
(3) preparation method of 4-azido-phenyl-4-hexyloxy benzene methyl (D) is with embodiment 2
(4) preparation of 4-acetylenylbenzene hexyl formate is with embodiment 1
(5) 4-[1-(4-(4-hexyloxy) carbobenzoxy) phenyl]-1H-[1,2,3]-triazol radical hexyl-benzoate (T
3) preparation with embodiment 1
Embodiment 4: preparation R
1Be n-hexyl, R
2For
Compound (T
4)
The preparation of (1) 1,4-two phenylazides is with embodiment 1
(2) preparation of 4-acetylenylbenzene hexyl formate is with embodiment 1
(3) 4,4`-(1-(1H-[1,2,3]-triazol radical)-1, the two phenyl of 4-) hexyl-benzoate (T
4) preparation with embodiment 1
Liquid crystal property is measured:
T
1The phase transition temperature that series compound is measured with DSC
Claims (2)
1. a class contains the triazole heterogeneous ring compound, it is characterized in that: the molecular structural formula of described compound is:
R wherein
1For: the straight chained alkyl of 2-12 carbon atom, branched-chain alkyl or chirality alkyl;
R wherein
2For: the straight chain ester group of 2-12 carbon atom, side chain ester group, chirality ester group, straight chain alkoxyl group, branched alkoxy, chirality alkoxyl group,
2. a class according to claim 1 contains the synthetic method of triazole heterogeneous ring compound, it is characterized in that: described compound is by synthesizing through the click chemistry method to the triazobenzene manthanoate and to the acetylenylbenzene manthanoate, and its synthesis step is as follows:
(1) be raw material with para-amino benzoic acid and dehydrated alcohol, the vitriol oil is made catalyzer, makes parathesin;
(2) under the ice-water bath condition, in molar ratio 1 part of parathesin is dissolved in 1 part of concentrated hydrochloric acid and the 1 part of water, add 2 parts of Sodium Nitrites after 10-30 minute, be incubated 0～5 ℃ 1-2 hour, slowly add 2 parts of sodiumazide, stopped reaction after 10-45 minute, filtration, washing, dry must be to the triazobenzene manthanoate;
(3) be that raw material prepares the parabromobenzoic acid ethyl ester through esterification with the parabromobenzoic acid;
(4) in molar ratio, with 10 parts of parabromobenzoic acid ethyl esters, 12 parts of 2-methyl-3-butyne-2-alcohols, 0.1 part of triphenylphosphine, 0.05 part of cuprous iodide, 0.01 part of bi triphenyl phosphine dichloride palladium and 15 parts of anhydrous triethylamines and 5 parts of pyridines, under nitrogen protection back flow reaction 1-3 hour, pour in the water, extract, cross the post separation and obtain 4-(3-hydroxy-3-methyl-1-propine) ethyl benzoate;
(5) in molar ratio, the adding of 10 parts of 4-(3-hydroxy-3-methyl-1-propine) ethyl benzoate is dissolved with in the Virahol of 40 parts of potassium hydroxide, backflow 1-5 hour, filtered while hot got the benzoic sylvite of 4-ethynyl;
(6) in molar ratio, 2 parts of benzoic sylvite of 4-ethynyl are suspended in 5-20 part chloroform, add 4-10 part sulfur oxychloride under the ice-water bath condition, steamed solvent in room temperature reaction 4-10 hour, add 2 parts of corresponding alcohol, methylene dichloride is made solvent, and refluxing under anhydrous pyridine catalysis makes 4-acetylenylbenzene manthanoate;
(7) with described to the triazobenzene manthanoate with the acetylenylbenzene manthanoate is made target product through the click chemistry method, mol ratios such as employing to triazobenzene manthanoate and 4-acetylenylbenzene manthanoate in the presence of 1 equivalent cupric sulfate pentahydrate and 3 normal sodium ascorbates, with the tetrahydrofuran (THF) and the water as solvent of equal-volume ratio, can obtain containing the triazole heterogeneous ring compound in room temperature reaction 8-72 hour.
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