CN1438209A - Method for preparing 4-methyl-tetrafluoro-benzil-alcohol - Google Patents
Method for preparing 4-methyl-tetrafluoro-benzil-alcohol Download PDFInfo
- Publication number
- CN1438209A CN1438209A CN 03121043 CN03121043A CN1438209A CN 1438209 A CN1438209 A CN 1438209A CN 03121043 CN03121043 CN 03121043 CN 03121043 A CN03121043 A CN 03121043A CN 1438209 A CN1438209 A CN 1438209A
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- Prior art keywords
- methyl
- alcohol
- reaction
- hydrogen
- tetrafluorobenzyl alcohol
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- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000000034 method Methods 0.000 title claims description 9
- 238000006722 reduction reaction Methods 0.000 claims abstract 4
- -1 4-methyl tetrafluorobenzyl alcohol Chemical compound 0.000 claims description 22
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims description 9
- 239000001257 hydrogen Substances 0.000 claims description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- 229910019142 PO4 Inorganic materials 0.000 claims 1
- 239000010452 phosphate Substances 0.000 claims 1
- 239000002994 raw material Substances 0.000 claims 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract description 8
- 125000002496 methyl group Chemical class [H]C([H])([H])* 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 241000209094 Oryza Species 0.000 description 3
- 235000007164 Oryza sativa Nutrition 0.000 description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 3
- 238000001953 recrystallisation Methods 0.000 description 3
- 235000009566 rice Nutrition 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000000967 suction filtration Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- ZFHGXWPMULPQSE-SZGBIDFHSA-N (Z)-(1S)-cis-tefluthrin Chemical compound FC1=C(F)C(C)=C(F)C(F)=C1COC(=O)[C@@H]1C(C)(C)[C@@H]1\C=C(/Cl)C(F)(F)F ZFHGXWPMULPQSE-SZGBIDFHSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229910010082 LiAlH Inorganic materials 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000005939 Tefluthrin Substances 0.000 description 2
- 150000001555 benzenes Chemical group 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 239000002917 insecticide Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 235000011007 phosphoric acid Nutrition 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000002728 pyrethroid Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- BWVAOONFBYYRHY-UHFFFAOYSA-N [4-(hydroxymethyl)phenyl]methanol Chemical compound OCC1=CC=C(CO)C=C1 BWVAOONFBYYRHY-UHFFFAOYSA-N 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- XGFJCRNRWOXGQM-UHFFFAOYSA-N hot-2 Chemical compound CCSC1=CC(OC)=C(CCNO)C=C1OC XGFJCRNRWOXGQM-UHFFFAOYSA-N 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 125000001037 p-tolyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention is a method of making 4-methyl fluorobenzoic alcohol, made by using 4-substituted methyl tetraflurobenzoic alcohol through hydrogenation-reduction reaction.
Description
Technical field:
The present invention relates to the preparation method of pyrethroid insecticides tefluthrin important intermediate 4-methyl tetrafluorobenzyl alcohol.
Background technology
4-methyl tetrafluorobenzyl alcohol is the important intermediate of synthetic pyrethroid insecticide tefluthrin, and GB2066810 has introduced a kind of LiAlH of using
4Directly reduction 4-tolyl acid prepares the method for 4-methyl tetrafluorobenzyl alcohol, yield 25%.What GB2155464 introduced is a kind of improving one's methods, and in the presence of quaternary ammonium salt, uses NaBH in water-organic solvent two-phase system
4Reduction 4-methyl phenyl tetrafluoride formyl chloride, yield 66%.Above-mentioned two kinds of methods all are to be reflected at the method for introducing the alcohol radical function on the substituted benzene ring by hydro-reduction to prepare 4-methyl tetrafluorobenzyl alcohol, and yield is also all on the low side.
Summary of the invention:
The objective of the invention is to introduce a kind of method of produced in high yields 4-methyl tetrafluorobenzyl alcohol.
Another object of the present invention is to introduce a kind of being reflected at by hydro-reduction to introduce the method that the methyl functional group prepares 4-methyl tetrafluorobenzyl alcohol on the substituted benzene ring.
The present invention finishes as follows:
The reaction formula that is prepared 4-methyl tetrafluorobenzyl alcohol by 4-replacement tetrafluorobenzyl alcohol hydro-reduction is:
X can be halogen, alkyl or aryl sulfonate radical, alkyl or aryl carboxylate radical, alkane stem or aryl phosphoric acids root in the formula.In the reaction process, can use the hydrogen atom of hydrogen, nascent state or compound metal hydroxide source as hydrogen.
The hydrogen atom of nascent state can produce by active metal such as sodium, magnesium, iron, zinc, aluminium etc. and acid effect, preferably selects zinc for use; Acid can be organic acid (as formic acid, acetate, propionic acid, phenylformic acid etc.), also can be mineral acid (example hydrochloric acid, sulfuric acid or phosphoric acid), preferably selects acetate for use.
The multiple hydrogen compound of metal can be NaBH
4, KBH
4Or LiAlH
4Deng, preferably select NaBH for use
4
If in the reaction process with the source of hydrogen as hydrogen, reaction is generally carried out in the presence of catalyzer, and catalyzer is to contain in the precious metals such as Ni, Pt, Pd, Co, Mo one or more, usefulness resin, gac, tripolite loading or not load, preferably select metal Pd for use, with activated carbon supported.
During reaction process was generally carried out in solvent, solvent can be to carry out among water, lower alcohol, the low-grade carboxylic acid, and preferred solvent is an acetate; Reaction pressure is 0～200atm, generally is 0～5atm; Temperature of reaction is 0～120 ℃, generally is 30～70 ℃; Reaction times is 0.5～10 hour, generally is 2～4 hours.
Reaction filters out catalyzer after finishing, and filtrate concentrates, and pours in the water, stirs moments later, and suction filtration, washing are promptly.
Embodiment
The several embodiment of various details further specify the present invention, but content of the present invention is not limited to therewith fully.
Embodiment 1
26.9g (0.01mol) the palladium charcoal of tetrafluoro terephthalyl alcohol monoacetate, 2.0g5% and 250ml acetate place autoclave pressure, with feeding hydrogen behind the air in the nitrogen replacement still, control pressure is 5atm, about 80 ℃ reactions of temperature 4 hours.Cooling, release, suction filtration, filtrate decompression concentrate, and pour 500ml water into after cold slightly, stir moments later suction filtration, washing, drying, and the sherwood oil recrystallization gets 18.6g rice white solid, MP60～62 ℃, yield 88%.
Embodiment 2
22.9g (0.10mol), the ethanol of 4-chloro methyl tetrafluorobenzyl alcohol, 16.3g zinc powder (0.25mol) and 100ml 50% places in the reaction flask, be heated to 60-65 ℃, drip 18g (0.30mol) acetic acid, drip off post-heating and refluxed filtered while hot 2 hours, the filtrate heating steams ethanol, cooling, filtration, washing, drying, sherwood oil recrystallization get 14.8g rice white solid, yield 76%.
Embodiment 3
5.0g (0.018mol) 4-bromomethyl tetrafluorobenzyl alcohol, 50ml methyl alcohol place Erlenmeyer flask, add 2.7g (0.072mol) sodium borohydride under the magnetic agitation, add in about 2 hours in batches, being heated to 50 ℃ stirred 8 hours, cooling drips a small amount of dilute hydrochloric acid, adds 100ml water and 100ml toluene again, after the stirring, tell toluene layer, volatilize solvent, the sherwood oil recrystallization, get 2.8g rice white solid, yield is 80%.
Claims (2)
1. the method for a hydro-reduction prepared in reaction 4-methyl tetrafluorobenzyl alcohol, it is characterized in that raw material is the 4-substituent methyl tetrafluorobenzyl alcohol with general formula (I) structure, X can be halogen, alkyl or aryl sulfonate radical, alkyl or aryl carboxylate radical, alkyl or aryl phosphate radical in the formula.
2. the method for a kind of hydro-reduction prepared in reaction 4-methyl tetrafluorobenzyl alcohol according to claim 1, the source that it is characterized in that hydrogen in the hydro-reduction reaction are the hydrogen of molecular state, the hydrogen atom or the multiple hydrogen compound of metal of nascent state.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03121043 CN1274653C (en) | 2003-03-21 | 2003-03-21 | Method for preparing 4-methyl-tetrafluoro-benzil-alcohol |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03121043 CN1274653C (en) | 2003-03-21 | 2003-03-21 | Method for preparing 4-methyl-tetrafluoro-benzil-alcohol |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1438209A true CN1438209A (en) | 2003-08-27 |
| CN1274653C CN1274653C (en) | 2006-09-13 |
Family
ID=27674250
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 03121043 Expired - Lifetime CN1274653C (en) | 2003-03-21 | 2003-03-21 | Method for preparing 4-methyl-tetrafluoro-benzil-alcohol |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1274653C (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013069810A1 (en) * | 2011-11-10 | 2013-05-16 | 住友化学株式会社 | Method for producing 4-hydroxymethyl-2,3,5,6-tetrafluorotoluene |
| CN106565421A (en) * | 2016-11-08 | 2017-04-19 | 岳阳中科华昂精细化工科技有限公司 | Preparation method of 2,3,5,6-tetrafluorohydrazine-1,4-benzene dimethanol |
| CN115215726A (en) * | 2021-04-19 | 2022-10-21 | 江苏优士化学有限公司 | Synthesis method of 4-methyl-2, 3,5, 6-tetrafluorobenzyl alcohol |
-
2003
- 2003-03-21 CN CN 03121043 patent/CN1274653C/en not_active Expired - Lifetime
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013069810A1 (en) * | 2011-11-10 | 2013-05-16 | 住友化学株式会社 | Method for producing 4-hydroxymethyl-2,3,5,6-tetrafluorotoluene |
| JP2013121950A (en) * | 2011-11-10 | 2013-06-20 | Sumitomo Chemical Co Ltd | Method for producing 4-hydroxymethyl-2,3,5,6-tetrafluorotoluene |
| CN103917510A (en) * | 2011-11-10 | 2014-07-09 | 住友化学株式会社 | The production method of 4-hydroxymethyl-2,3,5,6-tetrafluorotoluene |
| CN106565421A (en) * | 2016-11-08 | 2017-04-19 | 岳阳中科华昂精细化工科技有限公司 | Preparation method of 2,3,5,6-tetrafluorohydrazine-1,4-benzene dimethanol |
| CN106565421B (en) * | 2016-11-08 | 2019-04-26 | 岳阳中科华昂精细化工科技有限公司 | A kind of preparation method of 2,3,5,6-tetrafluoro-1,4-benzenedimethanol |
| CN115215726A (en) * | 2021-04-19 | 2022-10-21 | 江苏优士化学有限公司 | Synthesis method of 4-methyl-2, 3,5, 6-tetrafluorobenzyl alcohol |
| CN117776870A (en) * | 2021-04-19 | 2024-03-29 | 江苏优士化学有限公司 | Synthesis method of 4-methyl-2, 3,5, 6-tetrafluorobenzyl alcohol |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1274653C (en) | 2006-09-13 |
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Address after: 213022 No. 98 Minjiang Road, Xinbei District, Jiangsu, Changzhou Patentee after: JIANGSU AGROCHEM LABORATORY Co.,Ltd. Address before: 213022 No. 98 Minjiang Road, Changzhou New District, Jiangsu, Changzhou Patentee before: Farm Hormone Engineering Tech.-Research Center, Jiangsu |
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| CX01 | Expiry of patent term |
Granted publication date: 20060913 |
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| CX01 | Expiry of patent term |