CN1709844A - Method for producing substituted benzyl alcohol - Google Patents
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- CN1709844A CN1709844A CN 200510040610 CN200510040610A CN1709844A CN 1709844 A CN1709844 A CN 1709844A CN 200510040610 CN200510040610 CN 200510040610 CN 200510040610 A CN200510040610 A CN 200510040610A CN 1709844 A CN1709844 A CN 1709844A
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- substituted benzyl
- benzyl alcohol
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- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical class OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 title claims abstract description 103
- 235000019445 benzyl alcohol Nutrition 0.000 title claims abstract description 34
- 238000004519 manufacturing process Methods 0.000 title abstract description 3
- 238000000034 method Methods 0.000 claims abstract description 42
- -1 benzyl halide Chemical class 0.000 claims abstract description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical class O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 27
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 23
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical class O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 claims abstract description 9
- 239000002253 acid Substances 0.000 claims abstract description 7
- 238000000926 separation method Methods 0.000 claims abstract description 4
- 239000011261 inert gas Substances 0.000 claims abstract description 3
- 150000002367 halogens Chemical class 0.000 claims abstract 4
- 238000006243 chemical reaction Methods 0.000 claims description 20
- 229910052801 chlorine Inorganic materials 0.000 claims description 15
- 239000000460 chlorine Substances 0.000 claims description 15
- 229910052794 bromium Inorganic materials 0.000 claims description 6
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 4
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 4
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 4
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 3
- ZIHQUWYJSTVYAT-UHFFFAOYSA-N [NH-][N+]([O-])=O Chemical group [NH-][N+]([O-])=O ZIHQUWYJSTVYAT-UHFFFAOYSA-N 0.000 claims description 2
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 125000004104 aryloxy group Chemical group 0.000 claims description 2
- 239000012467 final product Substances 0.000 claims description 2
- 229910052740 iodine Inorganic materials 0.000 claims description 2
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 2
- 239000007795 chemical reaction product Substances 0.000 claims 1
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 23
- 230000007062 hydrolysis Effects 0.000 abstract description 20
- 239000003513 alkali Substances 0.000 abstract description 5
- 239000006227 byproduct Substances 0.000 abstract description 4
- 239000002904 solvent Substances 0.000 abstract description 4
- 230000002378 acidificating effect Effects 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract description 2
- 239000003054 catalyst Substances 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 33
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 22
- 239000012074 organic phase Substances 0.000 description 16
- 239000000047 product Chemical class 0.000 description 16
- 238000003756 stirring Methods 0.000 description 14
- 239000011541 reaction mixture Substances 0.000 description 12
- 229910052757 nitrogen Inorganic materials 0.000 description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 9
- 239000003921 oil Substances 0.000 description 9
- 239000007787 solid Substances 0.000 description 9
- 238000001953 recrystallisation Methods 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 description 6
- 229940073608 benzyl chloride Drugs 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 238000000605 extraction Methods 0.000 description 5
- 239000000706 filtrate Substances 0.000 description 5
- 238000003672 processing method Methods 0.000 description 5
- QSSXJPIWXQTSIX-UHFFFAOYSA-N 1-bromo-2-methylbenzene Chemical compound CC1=CC=CC=C1Br QSSXJPIWXQTSIX-UHFFFAOYSA-N 0.000 description 4
- JQZAEUFPPSRDOP-UHFFFAOYSA-N 1-chloro-4-(chloromethyl)benzene Chemical compound ClCC1=CC=C(Cl)C=C1 JQZAEUFPPSRDOP-UHFFFAOYSA-N 0.000 description 4
- MHDVGSVTJDSBDK-UHFFFAOYSA-N dibenzyl ether Chemical compound C=1C=CC=CC=1COCC1=CC=CC=C1 MHDVGSVTJDSBDK-UHFFFAOYSA-N 0.000 description 4
- 239000012452 mother liquor Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 229910000039 hydrogen halide Inorganic materials 0.000 description 3
- 239000012433 hydrogen halide Substances 0.000 description 3
- BASMANVIUSSIIM-UHFFFAOYSA-N 1-chloro-2-(chloromethyl)benzene Chemical compound ClCC1=CC=CC=C1Cl BASMANVIUSSIIM-UHFFFAOYSA-N 0.000 description 2
- DBHODFSFBXJZNY-UHFFFAOYSA-N 2,4-dichlorobenzyl alcohol Chemical compound OCC1=CC=C(Cl)C=C1Cl DBHODFSFBXJZNY-UHFFFAOYSA-N 0.000 description 2
- CAHQGWAXKLQREW-UHFFFAOYSA-N Benzal chloride Chemical class ClC(Cl)C1=CC=CC=C1 CAHQGWAXKLQREW-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 239000003905 agrochemical Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 229960004698 dichlorobenzyl alcohol Drugs 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000010931 ester hydrolysis Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- FVJIUQSKXOYFKG-UHFFFAOYSA-N (3,4-dichlorophenyl)methanol Chemical compound OCC1=CC=C(Cl)C(Cl)=C1 FVJIUQSKXOYFKG-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 238000006136 alcoholysis reaction Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000012264 purified product Substances 0.000 description 1
- 239000002728 pyrethroid Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 230000001131 transforming effect Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method for producing substituted benzyl alcohol. The method adopts substituted benzyl halide and water to directly carry out hydrolysis reaction under the protection of inert gas to generate substituted benzyl alcohol, and the substituted benzyl alcohol is separated and purified. The method does not use other substances as solvents in the hydrolysis process, does not use alkali or partially neutralize acidic byproducts, does not add catalysts, and can regenerate and use the generated halogen acid after separation and concentration.
Description
Technical field
The present invention relates to the production method of substituted benzyl alcohol, particularly relate to the method that adopts the reaction of substituted benzyl halogen direct hydrolysis to produce substituted benzyl alcohol.
Background technology
Benzyl halide hydrolysis reaction under the alkali effect prepares benzyl alcohol, extensively is seen in disclosed document, as Kirk-OthmerEncyclopedia of Chemical Technology, 5th ed., Jonh Weily ﹠amp; Sons, Inc., New York, 2001.Vol.6, pp.323～334.The processing method of being produced benzyl alcohol by benzyl chloride mainly contains two classes, and a class is a direct method, and the benzyl halide direct hydrolysis obtains benzyl alcohol; Another kind of is indirect method, and benzyl halide is converted into benzyl ester earlier, and hydrolysis or alcoholysis benzyl ester obtain benzyl alcohol again.Direct method such as US4474993 disclose the continuous processing method of benzyl chloride basic hydrolysis, and US5670029, US5728897 and US5750801 disclose separating and the continuous processing method of the alkali-free of hydrolysis benzyl chloride, solvent-free technology, reaction mixture.Indirect method such as US4283565 disclose the first system of benzyl halide manthanoate, afterwards alcohol solves the technology of benzyl alcohol.Can obtain multiple benzyl ester easily from other technology approach, the ester hydrolysis can obtain the high purity benzyl alcohol, as the disclosed method of US5883290, US6057482, US6326521B2 and US20010014762.Such benzyl ester hydrolysis process has superiority in all many-sides than indirect method.Therefore, direct method is worth further research and development.The hydrolysis reaction of benzyl halide need add usually alkali with in and hydrogen halide, faster carry out transforming more fully to impel reaction with reactant, and the reaction that benzyl halide and water are only arranged is a reversible, and those skilled in the art is known to this, referring to the US5728897 disclosed method.But a large amount of alkali of the continuous basic hydrolysis arts demand of benzyl chloride consumption produce salt and waste water, as the disclosed content of US4474993.Therefore, this technology has been carried out further exploring, as US5670029, US5728897 and the disclosed benzyl chloride hydrolysis process of US5750801, its remarkable advantage is a single step reaction, and is solvent-free, alkali-free, and yield height, benzyl chloride recycle and reclaim hydrogenchloride.
Substituted benzyl alcohol is used as intermediate, the medicated premix of multi-usage solvent, Minute Organic Synthesis and is used to prepare the compound with pharmaceutical active and agricultural chemical activity, is well known to a person skilled in the art.For example halogeno-benzyl alcohol is as the synthetic intermediate of pyrethroid.Obviously, because the structure diversity of substituted benzyl halogen and the extensive use of corresponding substituted benzyl alcohol thereof, hope can realize being produced by substituted benzyl halogen direct, the easy and eco-friendly processing method of substituted benzyl alcohol.
Summary of the invention
The purpose of this invention is to provide a kind of method of producing substituted benzyl alcohol with substituted benzyl halogen direct hydrolysis.
Technical scheme of the present invention is more much smaller than benzyl alcohol according to the solubleness of substituted benzyl alcohol in water shown in the formula (II), in the reaction process of formula (I) substituted benzyl halogen and water, product (II) and raw material (I) are in organic phase, water contains the product (II) of hydrogen halide and minute quantity, the reversed reaction degree is very weak, thereby makes this method for hydrolysis feasible technically.
The objective of the invention is to realize by following measures:
A kind of method of producing substituted benzyl alcohol, this method are to adopt the reaction that directly is hydrolyzed of substituted benzyl halogen and water, the generation substituted benzyl alcohol, and separation, purifying get final product;
Wherein substituted benzyl halogen is suc as formula shown in (I), and substituted benzyl alcohol is suc as formula shown in (II):
And, k represents an integer of 1～2, l represents an integer of 0～5, m represents an integer of 0～5, and n represents an integer of 0～4, (k+l+m+n) is an integer of 2～6, the substituting group that R represents is bromine, trifluoromethyl, itrile group, nitro, amide group, alkoxyl group or aryloxy, R can be identical or different, and X represents Cl, Br or I, and X can be identical or different.
Described method, wherein used substituted benzyl halogen are suc as formula shown in (III), and the substituted benzyl alcohol of generation is suc as formula shown in (IV):
?
Here, k, l, m, X are identical with above-mentioned definition.
Described method, wherein used substituted benzyl halogen are shown in formula V, and the substituted benzyl alcohol of generation is suc as formula shown in (VI):
?
Here, k, l, n, R, X are identical with above-mentioned definition.
Described method, wherein used substituted benzyl halogen are suc as formula shown in (VII), and the substituted benzyl alcohol of generation is suc as formula shown in (VIII):
?
Here, k, l, X are identical with above-mentioned definition.
Described method, wherein substituted benzyl halogen is suc as formula shown in (IX), and the corresponding substituted benzyl alcohol of generation is suc as formula shown in (X):
?
Here, l is identical with above-mentioned definition, and X is a chlorine or bromine; Further, l is 1,2 or 3, and X is a chlorine.
Substituted benzyl halogen of the present invention can adopt Industrial products.The hydrolysis of substituted benzyl halogen is carried out in the mode of direct hydrolysis, and substituted benzyl halogen mixes with the water of 5～200 times (moles), the water of preferred 10～150 times (moles), the water of preferred especially 20～100 times (moles).
Said mixture is reacting by heating in reactor, 40～320 ℃ of temperature ranges, preferred 70～220 ℃, preferred especially 90～180 ℃.
The pressure of reaction system is in liquid phase for keeping reaction system at least, and pressure range is 0～22.5 MPa, is preferably 0～10 MPa, preferred especially 0～5 MPa.
Adopting control of whipping appts and other supplementary unit and adjustment two-phase admixture and liquid flowing state is well known to a person skilled in the art.
According to the different technology conditions and the parameter of above-mentioned selection, the reaction times is from several minutes to several hours, and common 5～300 minutes, preferred 10～180 minutes, preferred especially 20～120 minutes.
Originally be reflected in normal pressure or the pressurized vessel and carry out; and by inert gas such as nitrogen protection; reaction mixture mainly is substituted benzyl alcohol, hydrogen halide, a small amount of dibenzyl ether and unconverted raw material; the mixture phase-splitting of stopped reaction; organic phase mainly is a substituted benzyl alcohol; water mainly is a haloid acid, and purified product reclaims haloid acid.The method of the method for separation, purifying substituted benzyl alcohol and recovery haloid acid is well known to a person skilled in the art.
The structure of different substituted benzyl halogen (I) and character have difference in various degree, therefore response feature can change, usually the electron-withdrawing substituent on the phenyl ring can make the replacement of monochloromethyl carry out easily, and the water solubility of product (II) is very little, help the reaction comparatively fast carry out higher with productive rate, by product ether is less.These are known in those skilled in the art.
Beneficial effect of the present invention:
The distinguishing feature of method of the present invention is that hydrolytic process does not have other material to make solvent, do not use in alkali neutralization or the part and acidic by-products, do not add catalyzer, resource consumption and waste discharge have been reduced, the haloid acid that generates is through separating and concentrating, renewable use has embodied Atom economy and eco-friendly process characteristic.
The substituted benzyl alcohol of multiple structure can be used as intermediate, the medicated premix of multi-usage solvent, Minute Organic Synthesis and is used to prepare compound with pharmaceutical active and agricultural chemical activity etc.
According to processing method of the present invention, the yield of products therefrom can reach 70～99%, can reach usually more than 90%, and by product is a dibenzyl ether, and unconverted (I) reclaims, and haloid acid separates and concentrates.
Embodiment
According to following embodiment, the present invention may be better understood.Yet, those skilled in the art will readily understand that the described concrete material proportion of embodiment, processing condition and result thereof only are used to illustrate the present invention, and should also can not limit the present invention described in detail.
The hydrolysis of embodiment 1:2-chlorobenzyl chloride
Add 2-chlorobenzyl chloride 48.3 grams to 1 liter autoclave pressure, 380 milliliters in water is used the nitrogen excluding air, and normal temperature places 1.5 MPas (to be gauge pressure nitrogen pressure, down together), stir, be rapidly heated 140 ℃, pressure 2.3 MPas, stirring reaction 80 minutes, stop heating, stir and cool to 60～70 ℃, pressure is reduced to normal pressure.Reclaim reaction mixture, toluene (60 milliliters * 2) is washed reactor, incorporates reaction mixture into.The organic phase of separate reacted mixture, water merges organic phase, anhydrous magnesium sulfate drying with toluene (100 milliliters * 2) extraction, cross filter solid, filtrate vacuum concentration to 70 milliliter adds 40 milliliters of sherwood oils, room temperature is placed, and separating out product is colourless tabular crystal, productive rate 76%.Water distill hydrochloric acid, raffinate contains 2-chlorine benzyl alcohol.Evaporated in vacuo raffinate, solid are integrated with the mother liquor of organic phase, evaporated in vacuo, and toluene-sherwood oil (1: 1) recrystallization gets second batch of product.
The hydrolysis (1) of embodiment 2:4-chlorobenzyl chloride
Add 4-chlorobenzyl chloride 19.3 grams to 250 milliliters of glass there-necked flasks, 150 milliliters in water, nitrogen protection is stirred, the backflow that is rapidly heated, stirring reaction 240 minutes stops heating, stirs and cool to 60～70 ℃, stops logical nitrogen.Reclaim reaction mixture, toluene (30 milliliters * 2) is washed reaction flask, incorporates reaction mixture into.The organic phase of separate reacted mixture, water merges organic phase, anhydrous magnesium sulfate drying with toluene (50 milliliters * 2) extraction, cross filter solid, the filtrate evaporated in vacuo adds 20 milliliters of toluene dissolvings, adds 20 milliliters of sherwood oils, room temperature is placed, and separates out the colourless tabular crystal of product, productive rate 81%.
The hydrolysis (2) of embodiment 3:4-chlorobenzyl chloride
Add 4-chlorobenzyl chloride 161 grams to 1 liter autoclave pressure, 450 milliliters in water is used the nitrogen excluding air, and normal temperature places 0.3 MPa with nitrogen pressure, stir, be rapidly heated 160 ℃, pressure 0.9 MPa, stirring reaction 10 minutes, stop heating, stir and cool to 60～70 ℃, pressure is reduced to normal pressure.Reclaim reaction mixture, toluene (60 milliliters * 2) is washed reactor, incorporates reaction mixture into.The organic phase of separate reacted mixture, water merges organic phase with toluene (100 milliliters * 2) extraction, and anhydrous magnesium sulfate drying is crossed filter solid, the filtrate evaporate to dryness.Raw material 47 grams are reclaimed in vacuum (100Pa) distillation.Be product at the bottom of the still,, get 4-chlorine benzyl alcohol 89 grams, yield 91% with toluene-sherwood oil recrystallization.Water distill hydrochloric acid, raffinate contains 4-chlorine benzyl alcohol.Evaporated in vacuo raffinate, solid are integrated with the mother liquor of organic phase, evaporated in vacuo, and toluene-sherwood oil (1: 1) recrystallization gets second batch of product.
The hydrolysis of embodiment 4:2-chlorine bromotoluene
The method of embodiment 1, raw material are 2-chlorine bromotoluene 55.2 grams, and product is a 2-chlorine benzyl alcohol, 20 minutes reaction times, productive rate 83%.
The hydrolysis of embodiment 5:4-chlorine bromotoluene
The method of embodiment 3, raw material are 4-chlorine bromotoluene 184 grams.95% transforms.The organic phase vacuum concentration, recrystallization gets 4-chlorine benzyl alcohol 119 grams, productive rate 89%.
Embodiment 6:2, the hydrolysis of 4-dichlorobenzyl chloride
Add 2 to 5 liters autoclave pressures, 4-dichlorobenzyl chloride 391 grams, 3000 milliliters in water is used the nitrogen excluding air, normal temperature places 0.1 MPa with nitrogen pressure, stirs, and is rapidly heated 130 ℃, pressure 0.3 MPa, stirring reaction 140 minutes stops heating, stirs and cool to 60～70 ℃, is depressurized to 0.Reclaim reaction mixture, toluene (200 milliliters * 2) is washed reactor, incorporates reaction mixture into.The organic phase of separate reacted mixture, water merges organic phase with toluene (500 milliliters * 2) extraction, and anhydrous magnesium sulfate drying is crossed filter solid, the filtrate evaporated in vacuo.Water distill hydrochloric acid, raffinate contains 2,4-dichloro benzyl alcohol, the evaporated in vacuo raffinate, solid is integrated with crude product.Raw material 62 grams are reclaimed in vacuum (100Pa) distillation.Be product at the bottom of the still,, get 2,4-dichloro benzyl alcohol 287 grams, yield 92% with toluene-sherwood oil (1: 1) recrystallization.The mother liquor evaporated in vacuo, toluene-sherwood oil (1: 1) recrystallization gets second batch of product.
Embodiment 7:3, the hydrolysis of 4-dichlorobenzyl chloride
The method of embodiment 6, raw material are 3, and the 4-dichlorobenzyl chloride gets product 3,4-dichloro benzyl alcohol 290 grams, yield 93%.
Embodiment 8:2,4, the hydrolysis of 6-three chlorobenzyl chlorides
Add 2,4 to 0.5 liter autoclave pressure, 6-three chlorobenzyl chlorides 54.5 grams, 360 milliliters in water, use the nitrogen excluding air, normal temperature places 1 MPa with nitrogen pressure, stirs, be rapidly heated 180 ℃, pressure 2.5 MPas, stirring reaction 30 minutes stops heating, stirring also cools to 60～70 ℃, and pressure is reduced to normal pressure.Reclaim reaction mixture, toluene (30 milliliters * 2) is washed reactor, incorporates reaction mixture into.The organic phase of separate reacted mixture, water merges organic phase with toluene (60 milliliters * 2) extraction, and anhydrous magnesium sulfate drying is crossed filter solid, the filtrate evaporate to dryness.Crude product gets 2,4 with toluene-sherwood oil recrystallization, 6-trichlorine benzyl alcohol 42.3 grams, productive rate 81%.Water distill hydrochloric acid, raffinate contains product.Evaporated in vacuo raffinate, solid are integrated with the mother liquor of organic phase, evaporated in vacuo, and toluene-sherwood oil (1: 1) recrystallization gets second batch of product.
Claims (10)
1. method of producing substituted benzyl alcohol is characterized in that this method is to adopt the reaction that directly is hydrolyzed under the situation of protection of inert gas of substituted benzyl halogen and water, the generation substituted benzyl alcohol, and separation, purifying get final product;
Wherein substituted benzyl halogen is suc as formula shown in (I), and substituted benzyl alcohol is suc as formula shown in (II):
And, k represents an integer of 1～2, l represents an integer of 0～5, m represents an integer of 0～5, n represents an integer of 0～4, (k+l+m+n) be an integer of 2～6, the substituting group that R represents is bromine, trifluoromethyl, itrile group, nitro, amide group, alkoxyl group or aryloxy, and X represents Cl, Br or I.
2. method according to claim 1 is characterized in that used substituted benzyl halogen suc as formula shown in (III), and the substituted benzyl alcohol of generation is suc as formula shown in (IV):
Here, k, l, m, X are identical with the definition in the claim 1.
3. according to the method for claim 1, it is characterized in that used substituted benzyl halogen shown in formula V, the substituted benzyl alcohol of generation is suc as formula shown in (VI):
Here, k, l, n, R, X are identical with the definition in the claim 1.
4. according to the method for claim 2, it is characterized in that used substituted benzyl halogen suc as formula shown in (VII), the substituted benzyl alcohol of generation is suc as formula shown in (VIII):
Here, k, l, X are identical with the definition in the claim 1.
5. according to the method for claim 4, it is characterized in that substituted benzyl halogen suc as formula shown in (IX), the corresponding substituted benzyl alcohol of generation is suc as formula shown in (X):
Here, l is identical with the definition in the claim 1, and X is a chlorine or bromine; Preferred l is 1,2 or 3, and X is a chlorine.
6. method according to claim 1 is characterized in that temperature of reaction is 40～320 ℃, is preferably 70～220 ℃, more preferably 90～180 ℃.
7. item method according to claim 1 is characterized in that reaction pressure 0～22.5 MPa, is preferably 0～10 MPa, more preferably 0～5 MPa.
8. method according to claim 1 is characterized in that the water yield in molar ratio for 5～200 times of substituted benzyl halogen amount, is preferably 10～150 times, more preferably 20～100 times.
9, method according to claim 1 is characterized in that the reaction times is 5～300 minutes, is preferably 10～180 minutes, more preferably 20～120 minutes.
10, method according to claim 1 is characterized in that reclaiming the haloid acid in the mixed reaction product.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200510040610 CN1709844A (en) | 2005-06-20 | 2005-06-20 | Method for producing substituted benzyl alcohol |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200510040610 CN1709844A (en) | 2005-06-20 | 2005-06-20 | Method for producing substituted benzyl alcohol |
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| CN1709844A true CN1709844A (en) | 2005-12-21 |
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