CN101550071A - Manufacturing method of 1,7,8-trifluoro-2-naphthol - Google Patents
Manufacturing method of 1,7,8-trifluoro-2-naphthol Download PDFInfo
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- CN101550071A CN101550071A CNA2008100869952A CN200810086995A CN101550071A CN 101550071 A CN101550071 A CN 101550071A CN A2008100869952 A CNA2008100869952 A CN A2008100869952A CN 200810086995 A CN200810086995 A CN 200810086995A CN 101550071 A CN101550071 A CN 101550071A
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- 238000004519 manufacturing process Methods 0.000 title claims abstract description 33
- XKDLQKJOTBECCW-UHFFFAOYSA-N 1,7,8-trifluoronaphthalen-2-ol Chemical compound C1=CC(F)=C(F)C2=C(F)C(O)=CC=C21 XKDLQKJOTBECCW-UHFFFAOYSA-N 0.000 title abstract 4
- 238000000034 method Methods 0.000 claims abstract description 20
- 150000001875 compounds Chemical class 0.000 claims abstract description 17
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 13
- 239000011737 fluorine Substances 0.000 claims abstract description 13
- YPWUQMKWNNQMDX-UHFFFAOYSA-N 1-fluoronaphthalene-2-carbaldehyde Chemical class C1=CC=C2C(F)=C(C=O)C=CC2=C1 YPWUQMKWNNQMDX-UHFFFAOYSA-N 0.000 claims description 38
- 238000006243 chemical reaction Methods 0.000 claims description 26
- 239000002904 solvent Substances 0.000 claims description 12
- 125000004432 carbon atom Chemical group C* 0.000 claims description 10
- 239000003586 protic polar solvent Substances 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- 150000002191 fatty alcohols Chemical class 0.000 claims description 5
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 239000004973 liquid crystal related substance Substances 0.000 abstract description 10
- BAOWVDHYZBLYMB-UHFFFAOYSA-N [F].C1=CC=NC=C1 Chemical compound [F].C1=CC=NC=C1 BAOWVDHYZBLYMB-UHFFFAOYSA-N 0.000 abstract description 5
- BAGQBTMEEISJLK-UHFFFAOYSA-N 2-fluoronaphthalene Chemical compound C1=CC=CC2=CC(F)=CC=C21 BAGQBTMEEISJLK-UHFFFAOYSA-N 0.000 abstract 1
- 239000013067 intermediate product Substances 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 19
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 18
- 239000007788 liquid Substances 0.000 description 17
- 239000000203 mixture Substances 0.000 description 13
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 11
- 238000004821 distillation Methods 0.000 description 11
- 229910052757 nitrogen Inorganic materials 0.000 description 11
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 239000003795 chemical substances by application Substances 0.000 description 9
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 9
- 229920006395 saturated elastomer Polymers 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000007086 side reaction Methods 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 238000002425 crystallisation Methods 0.000 description 5
- 230000008025 crystallization Effects 0.000 description 5
- 238000001819 mass spectrum Methods 0.000 description 5
- 235000002639 sodium chloride Nutrition 0.000 description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- 235000015320 potassium carbonate Nutrition 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000011780 sodium chloride Substances 0.000 description 4
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- GIEWZRKJKIKBDK-UHFFFAOYSA-N 2,3,4-trifluoronaphthalen-1-ol Chemical class C1=CC=C2C(O)=C(F)C(F)=C(F)C2=C1 GIEWZRKJKIKBDK-UHFFFAOYSA-N 0.000 description 3
- DWRCKZUQPWTXBU-UHFFFAOYSA-N 2,3-difluoronaphthalen-1-ol Chemical class C1=CC=C2C(O)=C(F)C(F)=CC2=C1 DWRCKZUQPWTXBU-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 238000013019 agitation Methods 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 239000012044 organic layer Substances 0.000 description 3
- 239000000741 silica gel Substances 0.000 description 3
- 229910002027 silica gel Inorganic materials 0.000 description 3
- 229960001866 silicon dioxide Drugs 0.000 description 3
- 235000017550 sodium carbonate Nutrition 0.000 description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
- 125000004417 unsaturated alkyl group Chemical group 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 125000001140 1,4-phenylene group Chemical group [H]C1=C([H])C([*:2])=C([H])C([H])=C1[*:1] 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- ZZLNZTUALLXMED-UHFFFAOYSA-N CCCOC1=CC2=C(C=CC=C2F)C=C1 Chemical class CCCOC1=CC2=C(C=CC=C2F)C=C1 ZZLNZTUALLXMED-UHFFFAOYSA-N 0.000 description 2
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000004334 fluoridation Methods 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 150000004780 naphthols Chemical class 0.000 description 2
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 2
- 235000011118 potassium hydroxide Nutrition 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 235000011121 sodium hydroxide Nutrition 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- JJMDTERTPNYIGZ-UHFFFAOYSA-N 2-cyclohexylacetaldehyde Chemical class O=CCC1CCCCC1 JJMDTERTPNYIGZ-UHFFFAOYSA-N 0.000 description 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 1
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001336 alkenes Chemical group 0.000 description 1
- 150000001350 alkyl halides Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 229950011260 betanaphthol Drugs 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- -1 clean 2 times Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 230000004069 differentiation Effects 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 235000012204 lemonade/lime carbonate Nutrition 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 235000014380 magnesium carbonate Nutrition 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 229960001708 magnesium carbonate Drugs 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- ORUIBWPALBXDOA-UHFFFAOYSA-L magnesium fluoride Chemical compound [F-].[F-].[Mg+2] ORUIBWPALBXDOA-UHFFFAOYSA-L 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- PVWOIHVRPOBWPI-UHFFFAOYSA-N n-propyl iodide Chemical compound CCCI PVWOIHVRPOBWPI-UHFFFAOYSA-N 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a manufacturing method of 1,7,8-trifluoro-2-naphthol. The method is used for manufacturing the 1,7,8-trifluoro-2-naphthol with fine purity by a single working procedure without adopting a special fluridizer, such as fluorine pyridinium, and the like. A solving means is as follows: a 3-fluoride naphthol derivative is manufactured in such a way that fluorine gas and a 2-fluoride naphthol derivative react. The 1,7,8-trifluoro-2-naphthol manufactured by the invention is useful for effectively manufacturing a manufactured intermediate product of 3-fluoronaphthalene liquid-crystal compounds.
Description
Technical field
The present invention relates to 1,7, the manufacture method efficiently of 8-three fluoro-beta naphthals, this compound is useful as the manufacturing intermediate of the liquid crystalline cpd that constitutes liquid-crystal composition.
Background technology
As liquid crystal display device, main all the time the use has the TN pattern or the STN pattern of torsion structure.Develop more is liquid crystalline cpd and the liquid-crystal composition with positive dielectric anisotropic that plays an important role in these systems all the time.On the other hand, one of shortcoming with display mode of above-mentioned torsion structure is that the visual angle is narrow and small, in order to improve this shortcoming, following display mode has been proposed: (1) make the liquid crystal molecule vertical orientation method (the VA pattern: Vertical Alignment (vertical alignment) pattern) or (2) by applying roughly parallel electric field with substrate, make liquid crystal molecule in the pattern of the face internal rotation parallel (IPS pattern: In-Plane Switching (exchange in the plane) pattern) etc. with substrate.In these modes, replace as liquid crystalline cpd with positive dielectric anisotropy and liquid-crystal composition with necessary compound of display mode of above-mentioned torsion structure, specific inductivity has proposed dielectric anisotropy and has been negative liquid crystalline cpd and liquid-crystal composition for negative liquid crystalline cpd and liquid-crystal composition occupies important effect.
For the above object, developed and had 1,7,8-three fluoronaphthalenes-2, the liquid crystalline cpd of 6-two bases discloses several compounds (with reference to patent documentation 1 and 2).But disclosed in these citing documents have 1,7,8-three fluoronaphthalenes-2, and the manufacture method of the liquid crystalline cpd of 6-two bases may not be efficiently, has therefore hindered the application of this liquid crystalline cpd.
In order to solve the problem that this liquid crystalline cpd is made, propose to use 1,7,8-three fluoro-beta naphthals are used as the manufacturing intermediate (with reference to patent documentation 3) of this liquid crystalline cpd.The manufacture method efficiently of this liquid crystalline cpd that uses this compound is disclosed in addition.
[changing 1]
In this citing document 1,7, in the manufacturing of 8-three fluoro-beta naphthals, use special fluorizating agent to be used for 7, the method for 8-two fluoro-beta naphthals.As special fluorizating agent, adopt fluorizating agent to the aromatic nucleus cationoid reaction, in this citing document, adopt the fluorine pyridinium salt.But this fluorizating agent is not only expensive, also has following problem.That is, as follows in the fluoridation of using the fluorine pyridinium salt, can't avoid the trifluoro naphthols further to be fluoridized and generate as 1,1,7 of main resultant or secondary resultant 8-tetrafluoro-1,2-dihydronaphthalene-2-ketone.
[changing 2]
Therefore, need will be in adopting the fluoridizing of this reaction generation 1,1,7,8-tetrafluoro-1,2-dihydronaphthalene-2-ketone reduces, and makes the operation of object, makes reaction process become miscellaneous.In addition, there are the problems such as generation of the chlorine side reaction of using from the resolvent of fluorizating agent or according to the kind of fluorizating agent that series solvent produces, thereby become 1,7, the obstacle in the manufacturing of 8-three fluoro-beta naphthals.
At above situation, expectation develops 1,7, the manufacture method efficiently of 8-three fluoro-beta naphthals.
Patent documentation 1: TOHKEMY 2001-31597 communique
Patent documentation 2: German patent application discloses No. 19522195
Patent documentation 3: the international brochure that discloses No. 2004/29015
Summary of the invention
The problem that invention will solve
The problem that the present application will solve is, a kind of special fluorizating agent such as fluorine pyridinium salt that do not adopt is provided, with single operation make purity good 1,7, the method for 8-three fluoro-beta naphthals.
The means of dealing with problems
The present application people etc. are in order to solve described problem, to various fluoridations with and reaction conditions study, found that, with with the difluoro naphthol derivative at the state of dissolution in low temperature in specific solvent, make fluorine gas and its reaction, the trifluoro naphthol derivative of generation is separated out, thereby 1 of difluoro naphthol derivative optionally can be fluoridized, finish the present application.
The present application provides with 1 of general formula (III) expression, 2, the manufacture method of 8-three fluoro-7-alkoxynaphtalene compounds, and provide with 1 of formula (II) expression, 7, the manufacture method of 8-three fluoro-beta naphthal compounds, described compound with formula (II) expression be, by will with formula (I) represent 7,8-two fluoro-beta naphthals are dissolved in the protic polar solvent, make fluorine gas and its reaction at-100 ℃ to-20 ℃, make generation usefulness formula (II) expression 1,7,8-three fluoro-beta naphthals are separated out, produce this compound, its etherificate is obtained the compound of representing with general formula (III)
[changing 3]
[changing 4]
[changing 5]
(in the formula, R represents the alkyl of carbonatoms 1 to 10.)
The invention effect
By manufacture method of the present invention, need not adopt the expensive and easy fluorizating agents that generate from the impurity of fluorizating agent such as fluorine pyridinium salt, just can make 1,7 efficiently, 8-three fluoro-beta naphthals with short operation.By the present application make 1,7,8-three fluoro-beta naphthals are that the manufacturing intermediate of liquid crystalline cpd is useful for making three fluoronaphthalenes efficiently.
Embodiment
Below, the present invention is described in detail.
What the present application had is characterized as, and adopts fluorine gas that naphthol derivative is fluoridized.Because fluorine gas is reactive high, therefore compared with using with simple substance, preferably it is diluted in the rare gas element and uses as mixed gas.
As rare gas element, can exemplify out nitrogen, rare gas etc.In addition, the concentration during as dilution is preferably below 30%.
In the present application, it is characterized by, utilize the solvability characteristic lower of fluoridizing the trifluoro naphthols that obtains than the solvability of difluoro naphthols, the low resultant of reaction of solubleness is separated out.Because the crystallization of separating out is not vulnerable to the influence of side reaction, therefore do not carry out the side reaction that causes by fluorine gas, can obtain object with good yield.Consider from this angle,, preferably use pure series solvent or carboxylic acid series solvent as the protic polar solvent.Pure series solvent as using can use all kinds of SOLVENTS, but is preferably a straight chain shape or a catenate Fatty Alcohol(C12-C14 and C12-C18), wherein, and the Fatty Alcohol(C12-C14 and C12-C18) of preferred carbonatoms 1 to 4, the more preferably straight-chain fatty alcohol of carbonatoms 1 to 3.As the carboxylic acid series solvent, a preferred straight chain shape or a catenate aliphatic carboxylic acid, wherein, the aliphatic carboxylic acid of preferred carbonatoms 1 to 5.In addition, the straight-chain fatty alcohol of further preferred carbonatoms 1 to 3, special particular methanol.
These solvents can be used alone, but also also mix together, if but to as 7 of starting raw material, the solvability of 8-two fluoro-beta naphthals is low, can prolong the reaction times, and therefore not preferred.In addition, if to as 1,7 of object, the solubleness of 8-three fluoro-beta naphthals is too high, can be difficult to suppress the carrying out of side reaction, and is therefore not preferred.
Because fluorine gas is reactive high, therefore, preferred reaction is carried out at low temperatures, and temperature of reaction is preferably-100 ℃ to-20 ℃, more preferably-100 ℃ extremely-60 ℃.
1,7, the etherificate of 8-three fluoro-beta naphthals is preferably reacted with haloalkane under alkaline condition.As alkali, can use mineral alkalis such as yellow soda ash, salt of wormwood, sodium hydroxide, potassium hydroxide, sodium bicarbonate, saleratus, magnesiumcarbonate, lime carbonate, preferred yellow soda ash, salt of wormwood, sodium hydroxide, potassium hydroxide, preferred especially yellow soda ash or salt of wormwood.
(application examples)
In the present application, make 1,2,8-three fluoro-7-alkoxynaphtalene compounds can be the manufacturing intermediate of liquid crystalline cpd and using suitably as three fluoronaphthalenes.
For example can exemplify out following manufacture method: with 1,2, after 3 lithiumations of 8-three fluoro-7-alkoxynaphtalene compounds, make itself and the cyclohexyl acetaldehyde derivatives reaction of representing with general formula (IV), obtain by with its dehydration, obtaining compound with general formula (VI) expression with leading to the alcohol that formula V is represented, further with alkene position hydrogenation
[changing 6]
(in the formula, R
1The expression carbonatoms 1～10 saturated or unsaturated alkyl, Y represent singly-bound ,-CH
2CH
2-or-CH
2O-, A represents anti-form-1,4-cyclohexylidene or 1,4-phenylene, n represent 0 or 1),
[changing 7]
(in the formula, X represents the saturated or unsaturated alkyl of carbonatoms 1～10, R
1The expression carbonatoms 1～10 saturated or unsaturated alkyl, Y represent singly-bound ,-CH
2CH
2-or-CH
2O-, A represents anti-form-1,4-cyclohexylidene or 1,4-phenylene, n represent 0 or 1).
[changing 8]
(in the formula, X, R
1, Y, A and n represent with compound (V) in X, the R of record
1, the meaning that Y, A are identical with n.)。
[embodiment]
Below, exemplify embodiment and illustrate in greater detail the present invention, but the present invention is not limited to these embodiment.The structure of compound waits and confirms by nuclear magnetic resonance spectrum (NMR), mass spectrum (MS).
(embodiment 1) 1,7, the manufacturing of 8-three fluoro-beta naphthals
[changing 9]
Under nitrogen atmosphere, in three mouthfuls of reactors of the 1000ml that possesses thermometer and whipping appts, add 7, methyl alcohol (350ml) solution of 8-two fluoro-beta naphthals (50g).Reaction system is cooled to-80 ℃ by liquid nitrogen, under agitation 100 minutes, is blown into the gas mixture of fluorine gas (10%)-nitrogen.After stopping the importing of gas mixture, stop cooling.After reaction finished, methyl alcohol was removed in underpressure distillation, added 250ml toluene and dissolved, and used the washing of saturated aqueous common salt, 250ml of 10% aqueous hydrochloric acid, the 250ml of 250ml clean successively.Underpressure distillation removes and desolvates, and obtains 1,7, the crystallization 41g (yield 75%) of 8-three fluoro-beta naphthals.
1H-NMR(CDCl
3)δ5.55(d，J＝1Hz，1H)，7.18-7.23(m，2H)，7.43-7.48(m，2H)
MS?m/z：198(M
+，100)
(comparative example 1) adopts N, N '-two fluoro-2,1,7 of 2 '-bipyridine salt, the manufacturing of 8-three fluoro-beta naphthals
[changing 10]
To 7, in acetonitrile (240ml) solution of 8-two fluoro-beta naphthals (26g), add N, N '-two fluoro-2,2 '-dipyridyl two (a tetrafluoro borate) (53g), reflux 3.5 hours.Reaction solution is poured in the water, separated organic layer, water layer is extracted 3 times with vinyl acetic monomer.Merge with organic layer, clean 2 times, concentrate, obtain as 1,1,7 of residue 8-tetrafluoro-1, the thick resultant of 2-dihydronaphthalene-2-ketone with saturated aqueous common salt.Residue before in autoclave, adding, 5% palladium-charcoal (moisture 50%, 5g), silica gel (5g) and vinyl acetic monomer (200ml), (4kg/cm under hydrogen pressure
2), stirred 4 hours under the room temperature.Use the sellaite filtering reacting liquid, concentrated filtrate.By the hexane/toluene mixing solutions residue is carried out recrystallization, obtain 1,7 of faint yellow crystallized form, 8-three fluoro-beta naphthals (25g).
91 ℃ of fusing points
1H-NMR (CDCl
3) δ 5.0-6.5 (broad peak, 1H), 7.14-7.24 (m, 2H), 7.45-7.55 (m, 2H)
MS?m/z：198(M
+，100)
(comparative example 2) utilizes acetonitrile solvent to carry out 1,7, the manufacturing of 8-three fluoro-beta naphthals
Under nitrogen atmosphere, in three mouthfuls of reactors of the 1000ml that possesses thermometer and whipping appts, add 7, acetonitrile (350ml) solution of 8-two fluoro-beta naphthals (50g).Reaction system is cooled to-20 ℃ by liquid nitrogen, under agitation 7 hours, is blown into the gas mixture of fluorine gas (10%)-nitrogen.After stopping the importing of gas mixture, stop cooling.After reaction finished, underpressure distillation removed and desolvates, and added 250ml toluene and dissolved, and used the washing of saturated aqueous common salt, 250ml of 10% aqueous hydrochloric acid, the 250ml of 250ml clean successively.Underpressure distillation removes and desolvates, and obtains tarry resultant.In order to remove the impurity that generates by side reaction, carry out wet distillation, obtain 1,7, the crystallization of 8-three fluoro-beta naphthals (yield 19%) 10.7g.In this reaction, except object, can also be recovered to 3g, 8-two fluoro-beta naphthals and 1g tetrafluoro naphthol derivative as 7 of raw material.
Shown in the reaction of comparative example, when acetonitrile was used as solvent, not only the generation of impurity was many, the poor yields of object, and can carry out side reaction, the refining difficulty of object.
(comparative example 3) utilizes 2,2,3, and 3-C3-Fluoroalcohol/acetonitrile mixed solvent carries out 1,7, the manufacturing of 8-three fluoro-beta naphthals
Under nitrogen atmosphere, in three mouthfuls of reactors of the 1000ml that possesses thermometer and whipping appts, add 7,2,2,3 of 8-two fluoro-beta naphthals (50g), 3-C3-Fluoroalcohol/acetonitrile (1: 1) mixed solvent (400ml) solution.Reaction system is cooled to-20 ℃ by liquid nitrogen, under agitation 2 hours, is blown into the gas mixture of fluorine gas (10%)-nitrogen.After stopping the importing of gas mixture, stop cooling.After reaction finished, underpressure distillation removed and desolvates, and added 250ml toluene and dissolved, and used the washing of saturated aqueous common salt, 250ml of 10% aqueous hydrochloric acid, the 250ml of 250ml clean successively.Underpressure distillation removes and desolvates, and obtains tarry resultant.Tarry resultant of reaction is carried out wet distillation, obtain the crystallization of 25g xanchromatic.The analytical results that obtains by gas-chromatography is, this crystallization is as 1,7 of object, and 8-three fluoro-beta naphthals account for 40%, and as 7 of raw material, 8-two fluoro-beta naphthals account for 55% mixture.From this result, find out, though in this reaction the reaction times be 2 hours, raw material 1/2nd the differentiation, can only obtain the object about about 10g.
Recognize from this reaction result,, in the system that object is not separated out, can not obtain object effectively under temperature of reaction even adopt pure series solvent.
(embodiment 2) 1,2, the manufacturing of 8-three fluoro-7-propoxy-naphthalenes
[changing 11]
In three mouthfuls of reactors of the 2000ml that possesses reflux exchanger, thermometer and whipping appts, add 1,7 of 230g, the iodo propane of 8-three fluoro-beta naphthals, 256g, salt of wormwood and the 800ml acetone of 241g under nitrogen atmosphere, refluxed 3 hours.Confirm 1,7 with gas-chromatography, after the disappearance of 8-three fluoro-beta naphthals, cooling, distillation under reduced pressure removes desolvates.In residue, add the 500ml hexane and dissolve, filter insoluble salt.By the refining organic layer of the silicagel column of 500g, clean silica gel with hexane.Distillation under reduced pressure removes desolvates, and distillation residue (150 ℃/900Pa), obtain 1,2,8-three fluoro-7-propoxy-naphthalene 258g.
MS?m/z：240(M
+，100)
1H-NMR (CDCl
3) δ 1.09 (t, J=7.3Hz, 3H), 1.83 (wide sextet, J=7.0Hz, 2H), 4.17 (t, J=6.6Hz, 2H), 7.21 (ddd, J=12.0,9.0,7.1Hz, 1H), 7.27 (t, J=8.3Hz, 1H), 7.48-7.53 (m, 1H), 7.54 (dt, J=9.0,1.7Hz, 1H)
Industrial application
According to 1,7 of the present application manufacturing, 8-trifluoro-2-naphthol and 1,2,8-, three fluoro-7-alkoxynaphtalenes, right Be that the manufacturing intermediate of liquid-crystal compounds is useful in high efficiency manufacture three fluoronaphthalenes.
Claims (6)
1. one kind with 1,2 of general formula (III) expression, the manufacture method of 8-three fluoro-7-alkoxynaphtalene compounds, it is, by will be with 7 of (I) expression, 8-two fluoro-beta naphthals be dissolved in the protic polar solvent, make the reaction of itself and fluorine gas at-100 ℃ to-20 ℃, make that usefulness the formula (II) of generation represents 1,7,8-three fluoro-beta naphthals are separated out, produce 1,7,8-three fluoro-beta naphthals, by its etherificate being obtained compound with general formula (III) expression
[Chemical formula 1]
[Chemical formula 2]
[chemical formula 3]
In the formula, R represents the alkyl of carbonatoms 1 to 10.
2. one kind with 1 of formula (II) expression, 7, the manufacture method of 8-three fluoro-beta naphthals, it is, by will be with 7 of (I) expression, 8-two fluoro-beta naphthals are dissolved in the protic polar solvent, make the reaction of itself and fluorine gas at-100 ℃ to-20 ℃, make that usefulness the formula (II) of generation represents 1,7,8-three fluoro-beta naphthals are separated out
[chemical formula 4]
[chemical formula 5]
3. manufacture method according to claim 1 and 2 wherein, as the protic polar solvent, adopts alcohol system or carboxylic acid series solvent.
4. manufacture method according to claim 1 and 2 wherein, is diluted in fluorine gas in the rare gas element and reacts.
5. manufacture method according to claim 3, wherein, temperature of reaction is-100 ℃ to-60 ℃.
6. manufacture method according to claim 5 wherein, as the protic polar solvent, adopts the Fatty Alcohol(C12-C14 and C12-C18) of carbonatoms 1 to 4.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103804154A (en) * | 2014-03-12 | 2014-05-21 | 石家庄诚志永华显示材料有限公司 | Midbody and method for preparing 1,7,8-trifluoro-2-alkoxynaphthalenel |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS606339B2 (en) * | 1979-04-28 | 1985-02-18 | ダイキン工業株式会社 | Fluorination method |
| DE19542148A1 (en) * | 1995-11-11 | 1997-05-15 | Hoechst Ag | Process for the preparation of fluorinated aromatics |
| TWI319762B (en) * | 2002-09-27 | 2010-01-21 | 1,7,8-trifluoro-2-naphthol and manufacturing methods for liquid crystal compositions containing the same |
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2008
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103804154A (en) * | 2014-03-12 | 2014-05-21 | 石家庄诚志永华显示材料有限公司 | Midbody and method for preparing 1,7,8-trifluoro-2-alkoxynaphthalenel |
| CN103804154B (en) * | 2014-03-12 | 2015-07-15 | 石家庄诚志永华显示材料有限公司 | Midbody and method for preparing 1,7,8-trifluoro-2-alkoxynaphthalenel |
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