CN102260223A - Serial-aristeromycin compounds containing 1,3-benzodiazole and synthesis method thereof - Google Patents

Serial-aristeromycin compounds containing 1,3-benzodiazole and synthesis method thereof Download PDF

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CN102260223A
CN102260223A CN201110154992XA CN201110154992A CN102260223A CN 102260223 A CN102260223 A CN 102260223A CN 201110154992X A CN201110154992X A CN 201110154992XA CN 201110154992 A CN201110154992 A CN 201110154992A CN 102260223 A CN102260223 A CN 102260223A
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methyl
difluoro
benzodiazole
ethyl
arh
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蒋海珍
杨昆
郝健
陆文峻
万文
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University of Shanghai for Science and Technology
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University of Shanghai for Science and Technology
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Abstract

The invention relates to serial-aristeromycin compounds containing 1,3-benzodiazole and a synthesis method thereof. The structural formula of the compounds is disclosed in the specification, wherein R is -COOEt-Ph, -COOCH3-Ph, -NO2-Ph, Ph, -OCH3-Ph, -CH3-Ph, -CH3-Ph, NO2-Ph, pyridine, (Z)-CH=CHCOOEt, (E)-CH=CHCOOEt or (E)-CH=CHPh; and X is O, S or NCH2CH2CH2CH3. Since the serial-aristeromycin compounds containing 1,3-benzodiazole have unique properties in the aspect of novel liquid crystal materials, the efficient synthesis of the compounds becomes very meaningful. The synthesis method is simple to operate, has the characteristic of short procedure, and is convenient for after-treatment.

Description

Contain 1,3-benzodiazole compound and synthetic method thereof together with difluoro methylene is placed in-line
Technical field
The present invention relates to a kind ofly contain 1,3-benzodiazole compound and preparation method thereof together with difluoro methylene is placed in-line.
Background technology
The fast development of liquid-crystal display has been substituted traditional cathode-ray tube display, has become the main product of current field of information display, and this also directly affects the fast development of liquid crystal material.Along with liquid-crystal display is drive on household electrical appliance boldly, the successful Application of family expenses large screen television has particularly had higher requirement to the quality of liquid crystal material.The various monomers that the first requires to form mixed liquid crystal have wideer liquid crystal phase transition temperature range.It two is to reduce the response speed that liquid crystal material viscosity improves indicating meter to the greatest extent as far as possible.It three is thereby that the dielectric anisotropy that increases liquid crystal material plays energy-conservation effect.It four is moderate double refractions.And the basic demand of high-end liquid-crystal display to liquid crystal material not only satisfied in the successful development and application of fluorinated liquid crystal material, and led the development trend of liquid crystal material.In these fluorinated liquid crystal materials, after introducing together with difluoro methylene on the bridge chain of liquid crystal molecule parent nucleus, the highly significant that influences to liquid crystal property is considered to play the effect of " art is good for strength ".This is not only because together with the electronegativity maximum in the periodic table of elements of the fluorine atom in the difluoro methylene, so the moment of dipole of carbon-fluorine bond is bigger, have very great help to improving dielectric anisotropy, also, help reducing the viscosity of liquid crystal material because two fluorine atoms of molecule center bridged bond difluoro methylene have reduced intermolecular interaction force.As compound A, its structure is as follows:
Figure 143241DEST_PATH_IMAGE001
；
Introduce the difluoro methylene structural unit in molecule after, can make the clearing point of material improve 10-15 K, and the dielectric anisotropy performance of material increases to some extent, viscosity reduces.As special material of new generation, cause people's attention just more and more, have broad application prospects.
Therefore developed with a bromine difluoro methyl replace 1,3-benzodiazole fluoro-building block and halogenated aryl hydrocarbon, alkene synthesize under the promotion of transition metal copper and a series ofly contain 1, the compound of 3-benzodiazole together with difluoro methylene is placed in-line.For this compounds, report is not arranged as yet at present.
Contain 1 for such together with difluoro methylene is placed in-line, the synthetic method of the compound of 3-benzodiazole, report as yet so far.
Summary of the invention
The object of the present invention is to provide a series of new compounds.
Two of purpose of the present invention is to provide the synthetic method of such new compound.
For achieving the above object, the present invention adopts following reaction mechanism:
Figure 198921DEST_PATH_IMAGE002
Wherein R is :-COOEt-Ph ,-COOCH 3-Ph ,-NO 2-Ph, Ph ,-OCH 3-Ph ,-CH 3-Ph ,-CH 3-Ph ,-NO 2-Ph, Pyridine, (Z)-CH=CHCOOEt, (E)-CH=CHCOOEt or (E)-CH=CHPh; X is: O, S or NCH 2CH 2CH 2CH 3
According to above-mentioned synthetic method, the present invention adopts following technical scheme:
A kind ofly contain 1 together with difluoro methylene is placed in-line, the compound of 3-benzodiazole is characterized in that the structure of this compounds is:
Figure 953251DEST_PATH_IMAGE003
Wherein, R is :-COOEt-Ph ,-COOCH 3-Ph ,-NO 2-Ph, Ph ,-OCH 3-Ph ,-CH 3-Ph ,-CH 3-Ph ,-NO 2-Ph, Pyridine, (Z)-CH=CHCOOEt, (E)-CH=CHCOOEt or (E)-CH=CHPh; X is: O, S or NCH 2CH 2CH 2CH 3
Above-mentioned contain 1 together with difluoro methylene is placed in-line a kind of the preparation, the preparation method of 3-benzodiazole compound, the concrete steps that it is characterized in that this method are: under the inert atmosphere, halides and the mol ratio of the heterocycle building block that contains bromine difluoro methyl replacement by 4:1～1:4 are dissolved in the polar solvent, the copper powder that adds catalyst levels, reacted 2-8 hour down at 0～100 ℃,, obtain product through separation and purification.
Above-mentioned halides is: iodo ethyl benzoate, iodo-benzoic acid methyl esters, nitro iodobenzene, iodobenzene, methoxyl group iodobenzene, methyl iodobenzene, iodine pyridine, iodoethane ethyl propenoate, iodoethylene benzene or monobromoethane ethyl propenoate.
Above-mentioned halides is: 4-Iodobenzoic acid ethyl ester, o-iodobenzoic acid methyl esters, to the nitro iodobenzene, to methoxyl group iodobenzene, 1-iodo-4-methylbenzene, 1-iodo-2-methylbenzene, 1-iodo-4-oil of mirbane, the 2-iodine pyridine, (Z)-ethyl-3-iodopropylene acid esters, (E)-ethyl-3-iodopropylene acid esters, (E)-(2-iodoethylene) benzene or (Z)-ethyl-3-bromopropylene acid esters.
Above-mentioned contain 1 together with difluoro methylene is placed in-line a kind of the preparation, the preparation method of the compound of 3-benzodiazole, it is characterized in that the described heterocycle building block that contains bromine difluoro methyl replacement is: 2-one bromine difluoro methyl 1,3-benzoxazole, 2-one bromine difluoro methyl-1-butyl-1,3-benzoglyoxaline or 2-one bromine difluoro methyl 1, the 3-benzothiazole.
Above-mentioned organic solvent is: methyl-sulphoxide or dimethyl formamide.
Of the present inventionly contain 1 together with difluoro methylene is placed in-line, the compound of 3-benzodiazole class is owing to showing special performance aspect the novel liquid crystal material, and therefore efficient synthetic this compounds becomes very meaningful.
The present invention with a homemade bromine difluoro methyl replace 1,3-benzodiazole class fluoro-building block obtains a series ofly containing 1, the compound of 3-benzodiazole together with difluoro methylene is placed in-line with the halides reaction under the effect of transition metal copper.Raw material of the present invention is easy to get, and (as long as a step) easy and simple to handle, productive rate is at 10-97%.This compounds has higher research and using value at the novel liquid crystal luminescent material.
Embodiment
General step is with 2-one bromine difluoro methyl 1, and the reaction conditions of 3-benzoxazole and 4-iodo ethyl benzoate is an example
Embodiment one: under the nitrogen protection; in being housed, 25 milliliter of two neck bottle of magneton add 414 milligrams of (1.5 mmole) 4-iodo ethyl benzoates; 248 milligrams of (1 mmole) 2-one bromine difluoro methyls 1,3-benzoxazole, 2 milliliters of methyl-sulphoxides; 64 milligrams of (1 mmole) copper powders; react stopped reaction after 4 hours under the room temperature, reaction solution is cooled to room temperature, directly uses silica gel column chromatography separating purification; obtain 32 milligrams of products, productive rate is 10%.The structure of this compound is:
Figure 752579DEST_PATH_IMAGE004
Chinese named: 4-(2-benzoxazolyl) difluoromethyl ethyl benzoate
English name: 4-(Benzooxazol-2-yl-difluoro-methyl)-benzoic acid ethyl
Molecular weight: 317.09
Outward appearance: white solid
Fusing point: 59-61 degree centigrade
Proton nmr spectra (500 MHz, CDCl 3) chemical shift (ppm of unit): δ8.17 (d, J=8.5 Hz, 2H, ArH), 7.80 (d, J=8.4 Hz, 3H, ArH), 7.59 (d, J=8.1 Hz, 1H, ArH), 7.38-7.46 (m, 2H, ArH), 4.40 (q, J=7.1 Hz, 2H ,-OCH 2-), 1.40 (t, J=7.1 Hz, 3H ,-CH 2CH 3);
Nucleus magnetic resonance fluorine spectrum (470 MHz, CDCl 3) chemical shift (ppm of unit): δ-96.01 (s, 2F)
Carbon-13 nmr spectra (125 MHz, CDCl 3) chemical shift (ppm of unit): δ165.7,158.0 (t, 2 J C-F=36.2 Hz), 140.1,137.6 (t, 2 J C-F=30.0 Hz), 133.2,130.1,127.1,126.0 (t, 3 J C-F=5.6 Hz), 125.5,121.6,116.1,114.2 (t, 1 J C-F=242.9 Hz), 111.5,61.5,14.4;
Infrared spectra (adopting the Perkin-Elmer983G infrared spectrometer, the KBr pressed disc method):
νmax(cm -1):?3068,?1715,?1616,?1576,?1452,?1276,?1100,?850,?749.
Embodiment two: under the nitrogen protection; in being housed, 25 milliliter of two neck bottle of magneton add 414 milligrams of (1.5 mmole) 4-iodo ethyl benzoates successively; 248 milligrams of (1 mmole) 2-one bromine difluoro methyls 1,3-benzoxazole, 10 milliliters of dimethyl formamides; 64 milligrams of (1 mmole) copper powders; react stopped reaction after 4 hours under the room temperature, reaction solution is cooled to room temperature, directly uses silica gel column chromatography separating purification; obtain 89 milligrams of products, productive rate is 28%.
Embodiment three: under the nitrogen protection; in being housed, 50 milliliter of two neck bottle of magneton add 1.1 gram (4 mmole) 4-iodo ethyl benzoates successively; 2 gram (8 mmole) 2-, one bromine difluoro methyl 1,3-benzoxazole, 35 milliliters of dimethyl formamides; 1.2 gram (18.4 mmole) copper powder; react stopped reaction after 8 hours under the room temperature, reaction solution is cooled to room temperature, directly uses silica gel column chromatography separating purification; obtain product 0.98 gram, productive rate is 77%.
Embodiment four: under the nitrogen protection; in being housed, 50 milliliter of two neck bottle of magneton add 1.7 gram (6 mmole) 4-iodo ethyl benzoates successively; 1 gram (4 mmole) 2-, one bromine difluoro methyl 1,3-benzoxazole, 30 milliliters of dimethyl formamides; 0.26 gram (4 mmole) copper powder; react stopped reaction after 8 hours under the room temperature, reaction solution is cooled to room temperature, directly uses silica gel column chromatography separating purification; obtain product 0.33 gram, productive rate is 26%.
Embodiment five: under the nitrogen protection; in being housed, 100 milliliter of two neck bottle of magneton add 3.4 gram (12 mmole) 4-iodo ethyl benzoates successively; 2 gram (8 mmole) 2-, one bromine difluoro methyl 1,3-benzoxazole, 60 milliliters of dimethyl formamides; 0.6 gram (9.2 mmole) copper powder; react stopped reaction after 2 hours under the room temperature, reaction solution is cooled to room temperature, directly uses silica gel column chromatography separating purification; obtain product 1.13 grams, productive rate is 55%.
Embodiment six: under the nitrogen protection; in being housed, 250 milliliter of two neck bottle of magneton add 17 gram (60 mmole) 4-iodo ethyl benzoates successively; 12.5 gram (50 mmole) 2-one bromine difluoro methyl 1,3-benzoxazole, 150 milliliters of dimethyl formamides; 7.5 gram (115 mmole) copper powder; 60 degrees centigrade are reacted stopped reaction after 4 hours down, and reaction solution is cooled to room temperature, directly uses silica gel column chromatography separating purification; obtain product 7.04 grams, productive rate is 55%.
Embodiment seven: under the nitrogen protection; in being housed, 2 liter of two neck bottle of magneton add 44 gram (160 mmole) 4-iodo ethyl benzoates successively; 60 gram (240 mmole) 2-, one bromine difluoro methyl 1,3-benzoxazole, 1500 milliliters of methyl-sulphoxides; 36 gram (560 mmole) copper powders; 100 degrees centigrade are reacted stopped reaction after 4 hours down, and reaction solution is cooled to room temperature, directly uses silica gel column chromatography separating purification; obtain product 40 grams, productive rate is 78%.
 
The structural formula of 2-(2-benzoxazolyl) difluoromethyl methyl benzoate is:
Figure 275965DEST_PATH_IMAGE005
English name: 2-(Benzooxazol-2-yl-difluoro-methyl)-benzoic acid methyl ester
Molecular weight: 303.07
Outward appearance: white solid
Fusing point: 109 degrees centigrade of 107 –
Proton nmr spectra (500 MHz, CDCl 3) chemical shift (ppm of unit): δ=8.02 (d, J=7.9 Hz, 1H, ArH), 7.99 (d, J=7.7 Hz, 1H, ArH), 7.76 (d, J=7.7 Hz, 1H, ArH), 7.62-7.65 (m, 2H, ArH), 7.35-7.44 (m, 2H, ArH), 3.65 (s, 3H ,-OCH 3);
Nucleus magnetic resonance fluorine spectrum (470 MHz, CDCl 3) chemical shift (ppm of unit): δ=-90.65 (s, 2F)
Carbon-13 nmr spectra (125 MHz, CDCl 3) chemical shift (ppm of unit): δ=166.7,159.4 (t, 2 J C-F=33.7 Hz), 150.3,140.4,133.2 (t, 2 J C-F=24.1 Hz), 132.2,131.3,130.1,127.2 (t, 3 J C-F=9.1 Hz), 126.6,125.2,121.3,114.0 (t, 1 J C-F=240.3 Hz), 111.5,52.6;
Infrared spectra (adopting the Perkin-Elmer983G infrared spectrometer, the KBr pressed disc method):
νmax(cm -1)：3066,?1719,?1600,?1452,?1273,?1033,?747.
2-[two fluoro-(4-nitro-phenyl)-methyl] structural formula of benzoxazole is:
Figure 768126DEST_PATH_IMAGE006
English name: 2-[Difluoro-(4-nitro-phenyl)-methyl]-benzooxazole
Molecular weight: 290
Outward appearance: white solid
Fusing point: 131-132 degree centigrade
Proton nmr spectra (500 MHz, CDCl 3) chemical shift (ppm of unit): δ8.36 (d, J=8.8 Hz, 2H, ArH), 7.94 (d, J=8.8 Hz, 2H, ArH), 7.80 (d, J=7.9 Hz, 1H, ArH), 7.61 (d, J=8.2 Hz, 1H, ArH), 7.40-7.49 (m, 2H, ArH);
Nucleus magnetic resonance fluorine spectrum (470 MHz, CDCl 3) chemical shift (ppm of unit): δ-95.86 (s, 2F);
Carbon-13 nmr spectra (125 MHz, CDCl 3) chemical shift (ppm of unit): δ=157.3 (t, 2 J C-F=35.6 Hz), 150.9,149.7,140.0,139.5 (t, 2 J C-F=26.1 Hz), 127.4 (t, 3 J C-F=5.6 Hz), 125.7,124.1,121.6,113.6 (t, 1 J C-F=243.6 Hz), 111.6;
Infrared spectra (adopting the Perkin-Elmer983G infrared spectrometer, the KBr pressed disc method):
νmax(cm -1)：3077,?1615,?1533,?1452,?1258,?1080,?854,?752.
The structural formula of 2-(difluorophenyl methyl) benzoxazole is:
Figure 9751DEST_PATH_IMAGE007
English name: 2-(Difluoro-phenyl-methyl)-benzooxazole
Molecular weight: 245.07
Outward appearance: white solid
Fusing point: 35-37 degree centigrade
Proton nmr spectra (500 MHz, CDCl 3) chemical shift (ppm of unit): δ7.82 (d, J=8.0 Hz, 1H, ArH), 7.74 (d, J=7.6 Hz, 2H, ArH), 7.59 (d, J=7.4 Hz, 1H, ArH), 7.48-7.55 (m, 3H, ArH), 7.38-7.46 (m, 2H, ArH);
Nucleus magnetic resonance fluorine spectrum (470 MHz, CDCl 3) chemical shift (ppm of unit): δ-95.31 (s, 2F);
Carbon-13 nmr spectra (125 MHz, CDCl 3) chemical shift (ppm of unit): δ158.6 (t, 2 J C-F=37.0 Hz), 150.9,140.2,133.7 (t, 2 J C-F=25.8 Hz), 131.3,128.8,126.9,125.8 (t, 3 J C-F=5.7 Hz), 125.4,121.5,114.6 (t, 1 J C-F=242.5 Hz), 111.5;
Infrared spectra (adopting the Perkin-Elmer983G infrared spectrometer, the KBr pressed disc method):
νmax(cm -1)：3067,?1616,?1573,?1451,?1261,?1082,?914,?774,?748.
2-[two fluoro-(4-p-methoxy-phenyl) methyl] structural formula of benzoxazole is:
Figure 347192DEST_PATH_IMAGE008
English name: 2-[Difluoro-(4-methoxy-phenyl)-methyl] benzooxazole
Molecular weight: 275.08
Outward appearance: white solid
Fusing point: 76 degrees centigrade of 75 –
Proton nmr spectra (500 MHz, CDCl 3) chemical shift (ppm of unit): δ7.81 (d, J=7.2 Hz, 1H, ArH), 7.64 (d, J=7.0 Hz, 2H, ArH), 7.59 (d, J=8.6 Hz, 1H, ArH), 7.38-7.45 (m, 2H, ArH), 6.99 (d, J=8.9 Hz, 2H, ArH), 3.84 (s, 3H ,-OCH 3);
Nucleus magnetic resonance fluorine spectrum (470 MHz, CDCl 3) chemical shift (ppm of unit): δ-93.63 (s, 2F);
Carbon-13 nmr spectra (125 MHz, CDCl 3) chemical shift (ppm of unit): δ161.8,158.9 (t, 2 J C-F=37.4 Hz), 150.9,140.2,127.4 (t, 3 J C-F=10.7 Hz), 126.8,125.8 (t, 2 J C-F=26.3 Hz), 125.3,121.5,114.7 (t, 1 J C-F=241.4 Hz), 114.2,111.5,55.5;
Infrared spectra (adopting the Perkin-Elmer983G infrared spectrometer, the KBr pressed disc method):
νmax(cm -1)：3004,?1615,?1519,?1454,?1255,?1045,?921,?753.
The structural formula of 2-fluorine o-tolyl Jia base benzoxazole is:
Figure 990663DEST_PATH_IMAGE009
English name: 2-(Difluoro-o-tolyl-methyl)-benzoxazole
Molecular weight: 259.08
Outward appearance: colourless oil liquid
Proton nmr spectra (500 MHz, CDCl 3) chemical shift (ppm of unit): δ7.82 (d, J=7.5 Hz, 1H, ArH), 7.72 (d, J=7.8 Hz, 1H, ArH), 7.60 (d, J=8.2 Hz, 1H, ArH), 7.33-7.47 (m, 4H, ArH), 7.28 (d, J=7.6 Hz, 1H, ArH), 2.37 (s, 3H ,-CH 3);
Nucleus magnetic resonance fluorine spectrum (470 MHz, CDCl 3) chemical shift (ppm of unit): δ-94.79 (s, 2F);
Carbon-13 nmr spectra (125 MHz, CDCl 3) chemical shift (ppm of unit): δ158.6 (t, 2 J C-F=36.3 Hz), 150.8,140.2,137.0,132.2,131.8 (t, 2 J C-F=23.3 Hz), 131.3,126.9,126.3 (t, 3 J C-F=10.7 Hz), 126.2,125.4,121.6,115.2 (t, 1 J C-F=242.2 Hz), 111.6,20.0;
Infrared spectra (adopting the Perkin-Elmer983G infrared spectrometer, the KBr pressed disc method):
νmax(cm -1)?3033,?,1613,?1557,?1452,?1243,?1067,?749.
(Z)-and ethyl-4-(2-benzoxazolyl)-4, the structural formula of 4-difluoro-2-butene alcohol is:
Figure 325829DEST_PATH_IMAGE010
English name: (Z)-ethyl-4-(benzooxazol-2-yl)-4,4-difluoro-but-2-enoate
Molecular weight: 267.07
Outward appearance: yellow oily liquid
Proton nmr spectra (500 MHz, CDCl 3) chemical shift (ppm of unit): δ7.76(d, J=7.7 Hz, 1H, ArH), 7.59(d, J=8.3 Hz, 1H, ArH), and 7.34-7.42(m, 2H, ArH), 6.57 (dd, J H-F=23.6 Hz, J 2=12.1 Hz, 1H ,-CF 2CH-), 6.35 (d, J=12.1 Hz, 1H ,-CHCO-), 3.99 (q, J=7.2 Hz, 2H ,-OCH 2-), 1.05 (t, J=7.5 Hz, 3H ,-CH 3);
Nucleus magnetic resonance fluorine spectrum (470 MHz, CDCl 3) chemical shift (ppm of unit): δ-88.99 (d, J H-F=11.4 Hz, 2F);
Carbon-13 nmr spectra (125 MHz, CDCl 3) chemical shift (ppm of unit): δ163.6,157.7 (t, 2 J C-F=32.8 Hz), 150.3,140.1,134.2 (t, 2 J C-F=29.9 Hz), 129.4 (t, 3 J C-F=8.3 Hz), 126.8,125.3,121.2,112.0 (t, 1 J C-F=237.7 Hz), 111.5,61.3,13.7;
Infrared spectra (adopting the Perkin-Elmer983G infrared spectrometer, the KBr pressed disc method):
νmax(cm -1)：3064,?1729,?1653,?1615,?1451,?1238,?1058,?749.
The 4-(2-benzoxazolyl)-4, the structural formula of 4-difluoro-2-butene acetoacetic ester is:
Figure 117068DEST_PATH_IMAGE011
English name: 4-Benzooxazol-2-yl-4,4-difluoro-but-2-enoic acid ethyl ester
Molecular weight: 267.07
Outward appearance: yellow oily liquid
Proton nmr spectra (500 MHz, CDCl 3) chemical shift (ppm of unit): δ7.82 (d, J=7.95 Hz, 1H, ArH), 7.62 (d, J=7.95 Hz, 1H, ArH), 7.41-7.49 (m, 2H, ArH), 7.22 (dt, J 1=15.8 Hz, J 2=11.4 Hz, 1H ,-CHCF 2-), 6.56 (dt, J 1=15.8 Hz, J 2=2.2 Hz, 1H ,-CHCO-), 4.27 (q, J=7.1 Hz, 2H ,-OCH 2-), 1.32 (t, J=7.1 Hz, 3H ,-CH 3);
Nucleus magnetic resonance fluorine spectrum (470 MHz, CDCl 3) chemical shift (ppm of unit): δ-97.84 (d, J H-F=10.1 Hz, 2F); Carbon-13 nmr spectra (125 MHz, CDCl 3) chemical shift (ppm of unit): δ=164.4,156.6 (t, 2 J C-F=33.9 Hz), 150.8,140.0,135.4 (t, 2 J C-F=25.9 Hz), 127.9 (t, 3 J C-F=7.8 Hz), 127.4,125.7,121.6,112.2 (t, 1 J C-F=239.6 Hz), 111.6,61.7,24.2;
Infrared spectra (adopting the Perkin-Elmer983G infrared spectrometer, the KBr pressed disc method):
νmax(cm -1)：3081,?1726,?1661,?1615,?1573,?1451,?1271,?1047,?749.
The structural formula of 2-(2-pyridyl-difluoromethyl) benzoxazole is:
Figure 195882DEST_PATH_IMAGE012
English name: 2-(Difluoro-pyridin-2-yl-methyl)-benzoxazole
Molecular weight: 246.06
Outward appearance: white solid
Fusing point: 118-120 degree centigrade
Proton nmr spectra (500 MHz, CDCl 3) chemical shift (ppm of unit): δ8.67 (d, J=4.7 Hz, 1H, ArH), 7.88-7.93 (m, 2H, ArH), 7.81 (d, J=7.5 Hz, 1H, ArH), 7.60 (d, J=8.1 Hz, 1H, ArH), 7.37-7.45 (m, 3H, ArH);
Nucleus magnetic resonance fluorine spectrum (470 MHz, CDCl 3) chemical shift (ppm of unit): δ-98.79 (s, 2F);
Carbon-13 nmr spectra (125 MHz, CDCl 3) chemical shift (ppm of unit): δ157.9 (t, 2 J C-F=34.9 Hz), 152.1 (t, 2 J C-F=28.3 Hz), 150.9,150.0,140.3,137.6,126.9,125.9,125.3,121.5,120.8 (t, 3 J C-F=3.6 Hz), 113.1 (t, 1 J C-F=242.6 Hz), 111.5;
Infrared spectra (adopting the Perkin-Elmer983G infrared spectrometer, the KBr pressed disc method):
νmax(cm -1)：3037,?1614,?1591,?1474,?1291,?1065,?920,?798,?748.
The structural formula of 2-(difluoro p-methylphenyl methyl) benzoxazole is:
Figure 756176DEST_PATH_IMAGE013
English name: 2-(Difluoro-p-tolyl-methyl)-benzooxazole
Molecular weight: 259.08
Outward appearance: white solid
Fusing point: 69-71 degree centigrade
Proton nmr spectra (500 MHz, CDCl 3) chemical shift (ppm of unit): δ7.82 (d, J=8.0 Hz, 1H, ArH), 7.58-7.61 (m, 3H, ArH), 7.38-7.45 (m, 2H, ArH), 7.30 (d, J=8.0 Hz, 2H, ArH), 2.41 (s, 3H ,-CH 3);
Nucleus magnetic resonance fluorine spectrum (470 MHz, CDCl 3) chemical shift (ppm of unit): δ-94.79 (s, 2F);
Carbon-13 nmr spectra (125 MHz, CDCl 3) chemical shift (ppm of unit): δ158.8 (t, 2 J C-F=37.2 Hz), 150.9,141.6,140.2,130.8 (t, 2 J C-F=25.4 Hz), 129.5,126.9,125.7 (t, 3 J C-F=5.5 Hz), 125.4,121.5,114.7 (t, 1 J C-F=242.3 Hz), 111.5,21.5;
Infrared spectra (adopting the Perkin-Elmer983G infrared spectrometer, the KBr pressed disc method):
νmax(cm -1)：3040,?1615,?1573,?1451,?1264,?1095,?827,?748.
2-(1,1-two fluoro-3-phenyl-allyl groups) structural formula of benzoxazole is:
English name: 2-(1,1-Difluoro-3-phenyl-allyl)-benzooxazole
Molecular weight: 271.08
Outward appearance: white solid
Fusing point: 57-58 degree centigrade
Proton nmr spectra (500 MHz, CDCl 3) chemical shift (ppm of unit): δ7.85 (d, J=7.3 Hz, 1H, ArH), 7.50 (d, J=7.7 Hz, 1H, ArH), 7.34-7.51 (m, 7H, ArH), 7.21 (dt, J 1=16.2 Hz, J 2=2.4 Hz, 1H ,-CHC 6H 5), 6.66 (dt, J 1=16.2 Hz, J 2=11.0 Hz ,-CF 2CH-);
Nucleus magnetic resonance fluorine spectrum (470 MHz, CDCl 3) chemical shift (ppm of unit): δ-94.52 (d, J=10.5 Hz, 2F);
Carbon-13 nmr spectra (125 MHz, CDCl 3) chemical shift (ppm of unit): δ158.1 (t, 2 J C-F=36.3 Hz), 150.8,140.2,136.8 (t, 3 J C-F=8.6 Hz), 134.1,129.8,128.9,127.7,127.0,125.4,121.4,119.5 (t, 2 J C-F=25.0 Hz), 113.6 (t, 1 J C-F=237.8 Hz), 111.5;
Infrared spectra (adopting the Perkin-Elmer983G infrared spectrometer, the KBr pressed disc method):
νmax(cm -1)：?3033,?1656,?1451,?1224,?1052,?979,?808,?763.
Ethyl-4-(2-(1-butyl-1H-benzimidazolyl-) difluoromethyl) benzoic structural formula is:
Figure 540779DEST_PATH_IMAGE015
English name: ethyl-4-((1-butyl-1H-benzoimidazol-2-yl) difluoromethyl) benzoate
Molecular weight: 372.16
Outward appearance: colourless oil liquid
Proton nmr spectra (500 MHz, CDCl 3) chemical shift (ppm of unit): δ8.17 (d, J=8.4 Hz, 2H, ArH), 7.80 (d, J=8.2 Hz, 1H, ArH), 7.73 (d, J=8.5 Hz, 2H, ArH), 7.28-7.43 (m, 3H, ArH), 4.41 (q, J=7.2 Hz, 2H ,-OCH 2), 4.32 (t, J=7.9 Hz, 2H ,-NCH 2-), 1.79-1.85 (m, 2H ,-NCH 2CH 2-), 1.40-1.47 (m, 2H ,-CH 2CH 3), 1.41 (t, J=7.2 Hz, 3H ,-OCH 2CH 3), 0.97 (t, J=7.4 Hz, 3H ,-CH 2CH 3);
Nucleus magnetic resonance fluorine spectrum (470 MHz, CDCl 3) chemical shift (ppm of unit): δ-89.02 (s, 2F);
Carbon-13 nmr spectra (125 MHz, CDCl 3) chemical shift (ppm of unit): δ165.9,146.5 (t, 2 J C-F=32.7 Hz), 141.6,139.0 (t, 2 J C-F=25.5 Hz), 135.9,132.8,129.8,126.4 (t, 3 J C-F=5.5 Hz), 124.6,123.0,121.5,117.2 (t, 1 J C-F=238.8 Hz), 110.4,61.4,45.2,32.1,20.3,14.4,13.8;
Infrared spectra (adopting the Perkin-Elmer983G infrared spectrometer, the KBr pressed disc method):
νmax(cm -1)：3066,?1721,?1474,?1455,?1275,?1080,?835,?746.
Ethyl-4-(2-benzothiazolyl) structural formula of difluoromethyl phenylformic acid is:
Figure 423284DEST_PATH_IMAGE016
English name: ethyl-4-(benzothiazol-2-yl-difluoromethyl) benzoate
Molecular weight: 333.06
Outward appearance: white solid
Fusing point: 34-35 degree centigrade
Proton nmr spectra (500 MHz, CDCl 3) chemical shift (ppm of unit): δ8.15 (d, J=8.4 Hz, 2H, ArH), 8.09 (d, J=8.0 Hz, 1H, ArH), 7.96 (d, J=7.7 Hz, 1H, ArH), 7.80 (d, J=8.5 Hz, 2H, ArH), 7.47-7.55 (m, 2H, ArH), 4.40 (q, J=7.1 Hz, 2H ,-OCH 2-), 1.40 (q, J=7.1 Hz, 2H ,-CH 2CH 3);
Nucleus magnetic resonance fluorine spectrum (470 MHz, CDCl 3) chemical shift (ppm of unit): δ-87.66 (s, 2F);
Carbon-13 nmr spectra (125 MHz, CDCl 3) chemical shift (ppm of unit): δ165.7,164.3 (t, 2 J C-F=36.3 Hz), 152.8,138.9 (t, 2 J C-F=26.7 Hz), 135.0,132.7,129.8,126.8,126.7,126.0 (t, 3 J C-F=5.5 Hz), 124.5,121.9,117.2 (t, 1 J C-F=242.7 Hz), 61.5,14.4;
Infrared spectra (adopting the Perkin-Elmer983G infrared spectrometer, the KBr pressed disc method):
νmax(cm -1)：3061,?1720,?1515,?1458,?1277,?1088,?835,?760。

Claims (6)

1. one kind contains 1 together with difluoro methylene is placed in-line, and the compound of 3-benzodiazole is characterized in that the structure of this compounds is:
Figure 201110154992X100001DEST_PATH_IMAGE001
Wherein, R is :-COOEt-Ph ,-COOCH 3-Ph ,-NO 2-Ph, Ph ,-OCH 3-Ph ,-CH 3-Ph ,-CH 3-Ph ,-NO 2-Ph, Pyridine, (Z)-CH=CHCOOEt, (E)-CH=CHCOOEt or (E)-CH=CHPh; X is: O, S or NCH 2CH 2CH 2CH 3
2. one kind prepares according to claims 1 are described and contains 1 together with difluoro methylene is placed in-line, the preparation method of 3-benzodiazole compound, the concrete steps that it is characterized in that this method are: under the inert atmosphere, halides and the mol ratio of the heterocycle building block that contains bromine difluoro methyl replacement by 4:1～1:4 are dissolved in the polar solvent, the copper powder that adds catalyst levels, reacted 2-8 hour down at 0～100 ℃,, obtain product through separation and purification.
3. contain 1 according to claims 2 are described together with difluoro methylene is placed in-line, the preparation method of the compound of 3-benzodiazole is characterized in that described halides is: iodo ethyl benzoate, iodo-benzoic acid methyl esters, nitro iodobenzene, iodobenzene, methoxyl group iodobenzene, methyl iodobenzene, iodine pyridine, iodoethane ethyl propenoate, iodoethylene benzene or monobromoethane ethyl propenoate.
4. contain 1 according to claims 2 are described together with difluoro methylene is placed in-line, the preparation method of the compound of 3-benzodiazole, it is characterized in that described halides is: 4-Iodobenzoic acid ethyl ester, o-iodobenzoic acid methyl esters, to the nitro iodobenzene, to methoxyl group iodobenzene, 1-iodo-4-methylbenzene, 1-iodo-2-methylbenzene, 1-iodo-4-oil of mirbane, the 2-iodine pyridine, (Z)-ethyl-3-iodopropylene acid esters, (E)-ethyl-3-iodopropylene acid esters, (E)-(2-iodoethylene) benzene or (Z)-ethyl-3-bromopropylene acid esters.
5. one kind prepares according to claims 2 are described and contains 1 together with difluoro methylene is placed in-line, the preparation method of the compound of 3-benzodiazole, it is characterized in that the described heterocycle building block that contains bromine difluoro methyl replacement is: 2-one bromine difluoro methyl 1,3-benzoxazole, 2-one bromine difluoro methyl-1-butyl-1,3-benzoglyoxaline or 2-one bromine difluoro methyl 1, the 3-benzothiazole.
6. contain 1 according to claims 2 are described together with difluoro methylene is placed in-line, the preparation method of the compound of 3-benzodiazole is characterized in that described organic solvent is: methyl-sulphoxide or dimethyl formamide.
CN201110154992XA 2011-06-10 2011-06-10 Serial-aristeromycin compounds containing 1,3-benzodiazole and synthesis method thereof Pending CN102260223A (en)

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103396379A (en) * 2013-07-11 2013-11-20 华南理工大学 5, 6-difluoro-benzothiazole and preparation method thereof
CN103664814A (en) * 2013-12-16 2014-03-26 上海大学 Conjugate of monobromo difluoro methyl substituted benzo 1,3-diazole and benzyl bromide compound and preparation method of conjugate
CN103992288A (en) * 2014-05-09 2014-08-20 上海大学 Difluroisofagomine-tandem bi-aromatic compounds and preparation method
CN104140400A (en) * 2014-07-15 2014-11-12 江阴市天顺彩印有限公司 Green fluorescent compound and synthetic method and application of green fluorescent compound
CN104692985A (en) * 2013-12-06 2015-06-10 中国科学院上海有机化学研究所 Synthetic method for alpha-aryl, heteroaryl or alkenyl-alpha, alpha-difluoroallyl structure under catalysis of palladium
CN106588901A (en) * 2016-11-01 2017-04-26 上海大学 Azo compounds containing gem-difluoro methylene and preparation method of azo compounds
CN106588807A (en) * 2016-11-01 2017-04-26 上海大学 Olefin compound containing gem-difluoro-methylene and preparing method thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
杨昆，等: "Cu促进的gem-二氟亚甲基串联的杂环化合物的合成", 《第十一届全国氟化学会议论文集》 *

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CN103396379A (en) * 2013-07-11 2013-11-20 华南理工大学 5, 6-difluoro-benzothiazole and preparation method thereof
CN104692985A (en) * 2013-12-06 2015-06-10 中国科学院上海有机化学研究所 Synthetic method for alpha-aryl, heteroaryl or alkenyl-alpha, alpha-difluoroallyl structure under catalysis of palladium
CN104692985B (en) * 2013-12-06 2019-05-17 中国科学院上海有机化学研究所 Palladium chtalyst synthesizes alpha-aromatic, heteroaryl or alkenyl-α, α-difluoro allylic structure method
CN103664814A (en) * 2013-12-16 2014-03-26 上海大学 Conjugate of monobromo difluoro methyl substituted benzo 1,3-diazole and benzyl bromide compound and preparation method of conjugate
CN103992288A (en) * 2014-05-09 2014-08-20 上海大学 Difluroisofagomine-tandem bi-aromatic compounds and preparation method
CN104140400A (en) * 2014-07-15 2014-11-12 江阴市天顺彩印有限公司 Green fluorescent compound and synthetic method and application of green fluorescent compound
CN106588901A (en) * 2016-11-01 2017-04-26 上海大学 Azo compounds containing gem-difluoro methylene and preparation method of azo compounds
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CN106588901B (en) * 2016-11-01 2019-10-11 上海大学 Containing the azo-compound and preparation method thereof together with difluoro methylene
CN106588807B (en) * 2016-11-01 2020-04-03 上海大学 Alkene compound containing gem-difluoromethylene and preparation method thereof

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