CN113651837B - Preparation method of 3, 3-trifluoropropanol - Google Patents
Preparation method of 3, 3-trifluoropropanol Download PDFInfo
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- CN113651837B CN113651837B CN202110955266.1A CN202110955266A CN113651837B CN 113651837 B CN113651837 B CN 113651837B CN 202110955266 A CN202110955266 A CN 202110955266A CN 113651837 B CN113651837 B CN 113651837B
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- 238000002360 preparation method Methods 0.000 title abstract description 20
- 239000002798 polar solvent Substances 0.000 claims abstract description 76
- 238000006243 chemical reaction Methods 0.000 claims abstract description 68
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 63
- 150000004795 grignard reagents Chemical class 0.000 claims abstract description 35
- 239000007818 Grignard reagent Substances 0.000 claims abstract description 34
- 238000000034 method Methods 0.000 claims abstract description 25
- CYXIKYKBLDZZNW-UHFFFAOYSA-N 2-Chloro-1,1,1-trifluoroethane Chemical compound FC(F)(F)CCl CYXIKYKBLDZZNW-UHFFFAOYSA-N 0.000 claims abstract description 22
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 22
- 230000003301 hydrolyzing effect Effects 0.000 claims abstract description 14
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 11
- 239000003999 initiator Substances 0.000 claims abstract description 10
- 239000011777 magnesium Substances 0.000 claims abstract description 10
- SJRJJKPEHAURKC-UHFFFAOYSA-N N-Methylmorpholine Chemical compound CN1CCOCC1 SJRJJKPEHAURKC-UHFFFAOYSA-N 0.000 claims description 78
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 78
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 60
- 238000003756 stirring Methods 0.000 claims description 48
- 239000000243 solution Substances 0.000 claims description 41
- 238000010992 reflux Methods 0.000 claims description 36
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 30
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 26
- 239000011259 mixed solution Substances 0.000 claims description 24
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 22
- 229910052757 nitrogen Inorganic materials 0.000 claims description 11
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- 239000003929 acidic solution Substances 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 4
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 3
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052794 bromium Inorganic materials 0.000 claims description 3
- RDHPKYGYEGBMSE-UHFFFAOYSA-N bromoethane Chemical compound CCBr RDHPKYGYEGBMSE-UHFFFAOYSA-N 0.000 claims description 3
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 claims description 3
- APQIUTYORBAGEZ-UHFFFAOYSA-N 1,1-dibromoethane Chemical compound CC(Br)Br APQIUTYORBAGEZ-UHFFFAOYSA-N 0.000 claims 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 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 235000019253 formic acid Nutrition 0.000 claims description 2
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 239000002994 raw material Substances 0.000 abstract description 13
- 239000002904 solvent Substances 0.000 abstract description 5
- 239000002253 acid Substances 0.000 abstract description 4
- 239000006227 byproduct Substances 0.000 abstract description 4
- 230000009471 action Effects 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 26
- 238000006460 hydrolysis reaction Methods 0.000 description 12
- 239000000047 product Substances 0.000 description 12
- 239000000126 substance Substances 0.000 description 11
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 9
- 238000001816 cooling Methods 0.000 description 9
- 238000001035 drying Methods 0.000 description 9
- 238000007789 sealing Methods 0.000 description 9
- 238000005303 weighing Methods 0.000 description 9
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 6
- 229910052740 iodine Inorganic materials 0.000 description 6
- 239000011630 iodine Substances 0.000 description 6
- FFTOUVYEKNGDCM-OWOJBTEDSA-N (e)-1,3,3-trifluoroprop-1-ene Chemical compound F\C=C\C(F)F FFTOUVYEKNGDCM-OWOJBTEDSA-N 0.000 description 5
- 230000002194 synthesizing effect Effects 0.000 description 5
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 4
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N Butyraldehyde Chemical compound CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 229910052731 fluorine Inorganic materials 0.000 description 4
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000011737 fluorine Substances 0.000 description 3
- 238000005984 hydrogenation reaction Methods 0.000 description 3
- 230000000977 initiatory effect Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000005935 nucleophilic addition reaction Methods 0.000 description 3
- 238000007344 nucleophilic reaction Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 150000004703 alkoxides Chemical class 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- VILAVOFMIJHSJA-UHFFFAOYSA-N dicarbon monoxide Chemical group [C]=C=O VILAVOFMIJHSJA-UHFFFAOYSA-N 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 150000003138 primary alcohols Chemical group 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 description 1
- 239000002879 Lewis base Substances 0.000 description 1
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 1
- -1 alcohol compound Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- LHCGBIFHSCCRRG-UHFFFAOYSA-N dichloroborane Chemical compound ClBCl LHCGBIFHSCCRRG-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 239000012761 high-performance material Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 150000002485 inorganic esters Chemical class 0.000 description 1
- 150000007527 lewis bases Chemical class 0.000 description 1
- 150000002681 magnesium compounds Chemical class 0.000 description 1
- 229910001425 magnesium ion Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000000269 nucleophilic effect Effects 0.000 description 1
- 150000002895 organic esters Chemical class 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 230000001766 physiological effect Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 150000003333 secondary alcohols Chemical group 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- 238000007039 two-step reaction Methods 0.000 description 1
- 239000010888 waste organic solvent Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F3/00—Compounds containing elements of Groups 2 or 12 of the Periodic Table
- C07F3/02—Magnesium compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/09—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F3/00—Compounds containing elements of Groups 2 or 12 of the Periodic Table
- C07F3/003—Compounds containing elements of Groups 2 or 12 of the Periodic Table without C-Metal linkages
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The application discloses a preparation method of 3, 3-trifluoropropanol, which belongs to the field of organic synthesis and comprises the following steps: (1) Under the action of an initiator, chlorotrifluoroethane and magnesium react in a polar solvent to prepare a Grignard reagent CF 3CH2 MgCl solution; (2) Reacting a Grignard reagent CF 3CH2 MgCl solution with formaldehyde in a polar solvent to obtain a CF 3CH2CH2 OMgCl solution; the polar solvent does not include water; (3) Adding acid into the CF 3CH2CH2 OMgCl solution, and hydrolyzing to obtain the 3, 3-trifluoro propanol. The method takes the chlorotrifluoroethane as the raw material to prepare the 3, 3-trifluoro propanol, the raw material is cheap and easy to obtain, the cost is low, the preparation process is safe, the reaction condition is mild, the yield of the 3, 3-trifluoro propanol is high, the byproducts are few, and the solvent can be recycled.
Description
Technical Field
The application relates to a preparation method of 3, 3-trifluoropropanol, belonging to the field of organic synthesis.
Background
Fluorine-containing alcohols are a class of compounds in which a hydrogen atom on a carbon in an organic alcohol is replaced with a fluorine atom. Compared with organic alcohol, the molecular structure of the fluorine-containing alcohol compound shows unique physical, chemical and physiological activities due to the existence of C-F bonds. The 3, 3-trifluoro propanol is an important trifluoromethyl block as one of fluorine-containing alcohols, can be used as an intermediate for synthesizing medicines and pesticides, and can also be used as a raw material or an intermediate for synthesizing high-performance materials, and has wide application prospect.
Literature Chemical Communications (Cambridge, united Kingdom), (4), 386-387;2002 reports a method for synthesizing 3, 3-trifluoropropanol by reacting 3, 3-trifluoropropene with dichloroborane, but the method is very severe in conditions, needs to be carried out at about-70 ℃ and has low operation safety.
U.S. Pat. Nos. 3, 5777184 and 3, 6111139 disclose a process for the synthesis of esters using 1-chloro-3, 3-trifluoropropene by first reacting with an alcohol and then hydrolytically synthesizing 3, 3-trifluoropropanol. In the method, the 1-chloro-3, 3-trifluoropropene is expensive, relatively unstable and easy to polymerize.
Chinese patent CN201110244835 discloses a process for obtaining 3, 3-trifluoropropanol by high pressure hydrogenation reduction of 3, 3-trifluoropropanal as a starting material in the presence of Raney Ni catalyst. The method has the advantages of high yield, expensive raw materials, low operation safety of the hydrogenation process and poor overall industrial application prospect.
Chinese patents CN201210286304 and CN201210286302, and CN201210286343 and CN201210286371, respectively, report that 2-bromo-3, 3-trifluoropropene is used as a raw material, first 3, 3-trifluoropropenyl methyl ether is produced, and then 3, 3-trifluoropropenyl methyl ether is hydrogenated under high pressure under the action of inorganic or organic ester and Raney Ni catalyst to produce 3, 3-trifluoropropanol. But the method has the advantages of expensive and difficult obtainment of raw materials, low operation safety of the hydrogenation process and low total yield (50% -60%) of the two-step reaction.
Chinese patent CN201510750757 discloses a process for preparing 3, 3-trifluoropropanol from 3, 3-trifluoropropene by pressurizing reaction with solvent, catalyst and acid-binding agent to obtain intermediate 2-bromo-3, 3-trifluoropropanol with yield of 85.7%. The method has the advantages of expensive and difficult acquisition of raw materials, high reaction pressure, production of a large amount of waste organic solvents and acid binding agents in the preparation process, and environmental friendliness.
Disclosure of Invention
In order to solve the problems, the preparation method of the 3, 3-trifluoropropanol is provided, wherein chlorotrifluoroethane is used as a raw material to prepare the 3, 3-trifluoropropanol, the raw material is cheap and easy to obtain, the cost is low, the preparation process is safe, the reaction condition is mild, the yield of the 3, 3-trifluoropropanol is high, the byproducts are few, and the solvent can be recycled.
According to one aspect of the present application, there is provided a method for preparing 3, 3-trifluoropropanol comprising the steps of:
(1) Under the action of an initiator, chlorotrifluoroethane and magnesium react in a polar solvent to prepare a Grignard reagent CF 3CH2 MgCl solution;
(2) Reacting a Grignard reagent CF 3CH2 MgCl solution with formaldehyde in a polar solvent to obtain a CF 3CH2CH2 OMgCl solution; the polar solvent does not include water;
(3) Adding an acidic solution into the CF 3CH2CH2 OMgCl solution, and hydrolyzing to obtain the 3, 3-trifluoropropanol.
Preferably, the molar ratio of said magnesium to said chlorotrifluoroethane is (1.05-1.2): 1.
Preferably, the magnesium is magnesium strips, magnesium chips or magnesium powder. Most preferably, the magnesium is magnesium powder.
Optionally, the initiator is at least one or more of iodine, bromine, methyl iodide, ethyl bromide, dibromoethane and ethyl orthosilicate.
Preferably, the initiator is iodine.
Optionally, the polar solvent is at least one or more of diethyl ether, tetrahydrofuran, methyltetrahydrofuran, toluene, N-methylmorpholine, N-dimethylaniline and pyridine.
Optionally, the polar solvent consists of tetrahydrofuran, toluene and N-methylmorpholine, wherein the volume ratio of the tetrahydrofuran to the toluene is (6-8) (1-2).
Optionally, the polar solvent in step (1) has a mass 3 to 20 times that of the chlorotrifluoroethane.
Preferably, the polar solvent in step (1) has a mass of 5 to 10 times that of the chlorotrifluoroethane.
Optionally, the polar solvent in step (2) has a mass of 0.5 to 5 times that of the formaldehyde.
Preferably, the polar solvent in step (2) has a mass of 1-2 times that of the formaldehyde.
Optionally, the acidic solution is at least one or more of hydrochloric acid, sulfuric acid, nitric acid, acetic acid, and formic acid.
Preferably, the acidic solution is hydrochloric acid.
Optionally, the preparation method of the 3, 3-trifluoropropanol comprises the following steps:
(1) Adding magnesium, a polar solvent and an initiator into a reaction container under the protection of nitrogen, dropwise adding a mixed solution of chlorotrifluoroethane and the polar solvent into the reaction container, stirring and refluxing for reaction for 1-3h, and preparing a Grignard reagent CF 3CH2 MgCl solution;
(2) Dropwise adding the mixed solution of formaldehyde and a polar solvent into the prepared mixed solution of the Grignard reagent CF 3CH2 M gCl, and stirring and refluxing for reaction for 1-2h to prepare a CF 3CH2CH2 OMgCl solution;
(3) Adding an acidic solution into the prepared CF 3CH2CH2 OMgCl solution, stirring and reacting for 1-2h, and hydrolyzing to obtain the 3, 3-trifluoropropanol.
Optionally, the reaction temperature of stirring reflux in the step (1) is 10-30 ℃ and the reaction pressure is 0-0.2MPa.
Optionally, the reaction temperature of stirring reflux in the step (2) is 20-50 ℃ and the reaction pressure is 0-0.1MPa.
In the present application, the "reaction vessel" is a reaction vessel.
The beneficial effects of the application include, but are not limited to:
1. According to the preparation method of the 3, 3-trifluoropropanol, the method takes the chlorotrifluoroethane as the raw material to prepare the 3, 3-trifluoropropanol, the preparation raw material is cheap and easy to obtain, the cost is low, the preparation process is safe, the reaction condition is mild, the yield of the 3, 3-trifluoropropanol is high, the byproducts are few, and the solvent can be recycled.
2. According to the preparation method of the 3, 3-trifluoropropanol, the chlorotrifluoroethane and magnesium react in the polar solvent by using the initiator, the magnesium atom is directly connected with carbon on the chlorine atom to form a polar covalent bond, at the moment, the carbon on the chlorine atom is an electronegative end, and MgCl is an electropositive end, so that a Grignard reagent CF 3CH2 MgCl solution capable of providing electron cloud and having Lewis base property is generated, a nucleophilic group is provided for subsequent hydrolysis to generate alcohol so as to attack carbonyl carbon atom on methanol, and a new route for synthesizing the 3, 3-trifluoropropanol is realized.
3. According to the preparation method of the 3, 3-trifluoropropanol, a Grignard reagent CF 3CH2 MgCl solution is reacted with formaldehyde, formaldehyde is used for ensuring that a primary alcohol structure in the 3, 3-trifluoropropanol is generated, positive charge Mg ions can be combined with carbonyl oxygen of the formaldehyde, the other part of the Grignard reagent attacks carbonyl carbon atoms of the formaldehyde to form a transition state, single electron transfer is carried out to generate alkoxide, acid is used for catalyzing and hydrolyzing MgCl groups to obtain primary alcohol and magnesium compounds, 3-trifluoropropanol is further obtained, and the carbonyl oxygen of the formaldehyde is fully combined with the Grignard reagent by limiting the dosage ratio of a polar solvent to the formaldehyde, so that the alkoxide conversion rate is improved, and the yield of the 3, 3-trifluoropropanol is further improved.
4. According to the preparation method of the 3, 3-trifluoropropanol, tetrahydrofuran, toluene and N-methylmorpholine are selected to form a polar solvent, the volume ratio of the polar solvent to the N-methylmorpholine is limited, the reaction initiation difficulty is avoided, the nucleophilic addition reaction in the step (1) and the step (2) is easier to initiate, the Grignard reagent CF 3CH2 MgCl solution can fully react with formaldehyde, the polar solvent combination is more economical and safer, and the production cost is low.
5. According to the preparation method of the 3, 3-trifluoropropanol, the nucleophilic reaction of formaldehyde and the Grignard reagent is easy to initiate by controlling the reaction temperature and the stirring time in the step (2), the reaction can be fully carried out, CF 3CH2CH2 OMgCl generated by the reaction is not easy to decompose, and the yield of the finally prepared 3, 3-trifluoropropanol is high.
Detailed Description
The present application is described in detail below with reference to examples, but the present application is not limited to these examples.
Unless otherwise indicated, the starting materials and catalysts in the examples of the present application were purchased commercially, wherein the hydrochloric acid concentration was analytically pure and the sealed stirrer was of the model CJ, wired New chemical machinery Co., ltd.
Example 1
The method specifically comprises the following steps:
(1) Drying a reaction kettle provided with a sealing stirrer, a cooling pipe, a constant-pressure dropping funnel and a reflux condenser, adding 1.1mol of magnesium powder, 500ml of polar solvent (the volume ratio of the polar solvent is tetrahydrofuran: toluene: N-methylmorpholine=6:2:2) and 0.5mol of iodine into the reaction kettle under the protection of nitrogen, dropwise adding 1mol of chlorotrifluoroethane and 500ml of polar solvent (the volume ratio of the polar solvent is tetrahydrofuran: toluene: N-methylmorpholine=6:2:2) into the reaction kettle, stirring and refluxing for 2 hours at 10 ℃ and 0.1MPa, and preparing a Grignard reagent CF 3CH2 MgCl solution;
(2) Dropwise adding 1mol of mixed solution of formaldehyde and a polar solvent into the mixed solution of the Grignard reagent CF 3CH2 MgCl prepared in the step (1) by using a constant pressure dropping funnel, wherein the dropwise adding rate is 5ml/min, and stirring and refluxing at 20 ℃ and 0.05MPa for 2h, and the stirring rate is 100r/min to prepare a CF 3CH2CH2 OMgCl solution;
(3) Adding 2mol of hydrochloric acid into the CF 3CH2CH2 OMgCl solution prepared in the step (2), stirring and reacting for 1.5h, and hydrolyzing to obtain 3, 3-trifluoropropanol;
(4) After the hydrolysis reaction is completed, the product is rectified to obtain 3, 3-trifluoro propanol, and the yield is calculated by weighing.
Example 2
The method specifically comprises the following steps:
(1) Drying a reaction kettle provided with a sealing stirrer, a cooling pipe, a constant-pressure dropping funnel and a reflux condenser, adding 1.05mol of magnesium powder, 500ml of polar solvent (the volume ratio of the polar solvent is tetrahydrofuran: toluene: N-methylmorpholine=6:2:2) and 0.5mol of iodine into the reaction kettle under the protection of nitrogen, dropwise adding 1mol of chlorotrifluoroethane and 500ml of polar solvent (the volume ratio of the polar solvent is tetrahydrofuran: toluene: N-methylmorpholine=6:2:2) into the reaction kettle, stirring and refluxing for 2 hours at 20 ℃ and 0.05MPa, and preparing a Grignard reagent CF 3CH2 MgCl solution;
(2) Dropwise adding 1mol of mixed solution of formaldehyde and a polar solvent into the mixed solution of the Grignard reagent CF 3CH2 MgCl prepared in the step (1) by using a constant pressure dropping funnel, wherein the dropwise adding rate is 5ml/min, and stirring and refluxing at 30 ℃ and 0.05MPa for 2h, and the stirring rate is 100r/min to prepare a CF 3CH2CH2 OMgCl solution;
(3) Adding 2.2mol of hydrochloric acid into the CF 3CH2CH2 OMgCl solution prepared in the step (2), stirring and reacting for 1h, and hydrolyzing to obtain 3, 3-trifluoropropanol;
(4) After the hydrolysis reaction is completed, the product is rectified to obtain 3, 3-trifluoro propanol, and the yield is calculated by weighing.
Example 3
The method specifically comprises the following steps:
(1) Drying a reaction kettle provided with a sealing stirrer, a cooling pipe, a constant-pressure dropping funnel and a reflux condenser, adding 1.2mol of magnesium powder, 500ml of polar solvent (the volume ratio of the polar solvent is tetrahydrofuran: toluene: N-methylmorpholine=6:2:2) and 0.5mol of iodine into the reaction kettle under the protection of nitrogen, dropwise adding 1mol of chlorotrifluoroethane and 500ml of polar solvent (the volume ratio of the polar solvent is tetrahydrofuran: toluene: N-methylmorpholine=6:2:2) into the reaction kettle, stirring and refluxing for 3 hours at 30 ℃ and 0.2MPa, and preparing a Grignard reagent CF 3CH2 MgCl solution;
(2) Dropwise adding 1mol of mixed solution of formaldehyde and a polar solvent into the mixed solution of the Grignard reagent CF 3CH2 MgCl prepared in the step (1) by using a constant pressure dropping funnel, wherein the dropwise adding rate is 5ml/min, and stirring and refluxing at 40 ℃ and 0.1MPa for 2h, and the stirring rate is 100r/min to prepare a CF 3CH2CH2 OMgCl solution;
(3) Adding 2mol of hydrochloric acid into the CF 3CH2CH2 OMgCl solution prepared in the step (2), stirring and reacting for 2 hours, and hydrolyzing to obtain 3, 3-trifluoropropanol;
(4) After the hydrolysis reaction is completed, the product is rectified to obtain 3, 3-trifluoro propanol, and the yield is calculated by weighing.
Example 4
The method specifically comprises the following steps:
(1) Drying a reaction kettle provided with a sealing stirrer, a cooling pipe, a constant-pressure dropping funnel and a reflux condenser, adding 1.1mol of magnesium powder, 500ml of polar solvent (the volume ratio of the polar solvent is tetrahydrofuran: toluene: N-methylmorpholine=7:1.5:1.5) and 0.5mol of methyl iodide into the reaction kettle under the protection of nitrogen, dropwise adding 1mol of chlorotrifluoroethane and 500ml of polar solvent (the volume ratio of the polar solvent is tetrahydrofuran: toluene: N-methylmorpholine=7:1.5:1.5) into the reaction kettle, stirring and refluxing for 2 hours at 10 ℃ and 0.1MPa, and preparing a Grignard reagent CF 3CH2 MgCl solution;
(2) Dropwise adding 1mol of mixed solution of formaldehyde and a polar solvent into the mixed solution of the Grignard reagent CF 3CH2 MgCl prepared in the step (1) by using a constant pressure dropping funnel, wherein the dropwise adding rate is 5ml/min, and stirring and refluxing at 40 ℃ and 0MPa for 2h, and the stirring rate is 100r/min to prepare a CF 3CH2CH2 OMgCl solution;
(3) Adding 2mol of hydrochloric acid into the CF 3CH2CH2 OMgCl solution prepared in the step (2), stirring and reacting for 1.5h, and hydrolyzing to obtain 3, 3-trifluoropropanol;
(4) After the hydrolysis reaction is completed, the product is rectified to obtain 3, 3-trifluoro propanol, and the yield is calculated by weighing.
Example 5
The method specifically comprises the following steps:
(1) Drying a reaction kettle provided with a sealing stirrer, a cooling pipe, a constant-pressure dropping funnel and a reflux condenser, adding 1.1mol of magnesium powder, 500ml of polar solvent (the volume ratio of the polar solvent is tetrahydrofuran: toluene: N-methylmorpholine=7:1.5:1.5) and 0.5mol of iodine into the reaction kettle under the protection of nitrogen, dropwise adding 1mol of chlorotrifluoroethane and 500ml of polar solvent (the volume ratio of the polar solvent is tetrahydrofuran: toluene: N-methylmorpholine=7:1.5:1.5) into the reaction kettle, stirring and refluxing for 2 hours at 20 ℃ and 0.1MPa, and preparing a Grignard reagent CF 3CH2 MgCl solution;
(2) Dropwise adding 1mol of mixed solution of formaldehyde and a polar solvent into the mixed solution of the Grignard reagent CF 3CH2 MgCl prepared in the step (1) by using a constant pressure dropping funnel, wherein the dropwise adding rate is 5ml/min, and stirring and refluxing at 20 ℃ and 0.05MPa for 2h, and the stirring rate is 100r/min to prepare a CF 3CH2CH2 OMgCl solution;
(3) Adding 2mol of hydrochloric acid into the CF 3CH2CH2 OMgCl solution prepared in the step (2), stirring and reacting for 1.5h, and hydrolyzing to obtain 3, 3-trifluoropropanol;
(4) After the hydrolysis reaction is completed, the product is rectified to obtain 3, 3-trifluoro propanol, and the yield is calculated by weighing.
Example 6
The method specifically comprises the following steps:
(1) Drying a reaction kettle provided with a sealing stirrer, a cooling pipe, a constant-pressure dropping funnel and a reflux condenser, adding 1.1mol of magnesium powder, 500ml of polar solvent (the volume ratio of the polar solvent is tetrahydrofuran: toluene: N-methylmorpholine=7:1.5:1.5) and 0.5mol of bromine into the reaction kettle under the protection of nitrogen, dropwise adding 1mol of chlorotrifluoroethane and 500ml of polar solvent (the volume ratio of the polar solvent is tetrahydrofuran: toluene: N-methylmorpholine=7:1.5:1.5) into the reaction kettle, stirring and refluxing for 2 hours at 30 ℃ and 0.1MPa, and preparing a Grignard reagent CF 3CH2 MgCl solution;
(2) Dropwise adding 1mol of mixed solution of formaldehyde and a polar solvent into the mixed solution of the Grignard reagent CF 3CH2 MgCl prepared in the step (1) by using a constant pressure dropping funnel, wherein the dropwise adding rate is 5ml/min, and stirring and refluxing at 30 ℃ and 0.1MPa for 2h, and the stirring rate is 100r/min to prepare a CF 3CH2CH2 OMgCl solution;
(3) Adding 2mol of hydrochloric acid into the CF 3CH2CH2 OMgCl solution prepared in the step (2), stirring and reacting for 1.5h, and hydrolyzing to obtain 3, 3-trifluoropropanol;
(4) After the hydrolysis reaction is completed, the product is rectified to obtain 3, 3-trifluoro propanol, and the yield is calculated by weighing.
Example 7
The method specifically comprises the following steps:
(1) Drying a reaction kettle provided with a sealing stirrer, a cooling pipe, a constant-pressure dropping funnel and a reflux condenser, adding 1.1mol of magnesium powder, 500ml of polar solvent (the volume ratio of the polar solvent is tetrahydrofuran: toluene: N-methylmorpholine=8:1:1) and 0.5mol of iodine into the reaction kettle under the protection of nitrogen, dropwise adding 1mol of chlorotrifluoroethane and 500ml of polar solvent (the volume ratio of the polar solvent is tetrahydrofuran: toluene: N-methylmorpholine=8:1:1) into the reaction kettle, stirring and refluxing for 2 hours at 10 ℃ and 0.1MPa, and preparing a Grignard reagent CF 3CH2 MgCl solution;
(2) Dropwise adding 1mol of mixed solution of formaldehyde and a polar solvent into the mixed solution of the Grignard reagent CF 3CH2 MgCl prepared in the step (1) by using a constant pressure dropping funnel, wherein the dropwise adding rate is 5ml/min, and stirring and refluxing at 30 ℃ and 0.05MPa for 2h, and the stirring rate is 100r/min to prepare a CF 3CH2CH2 OMgCl solution;
(3) Adding 2mol of hydrochloric acid into the CF 3CH2CH2 OMgCl solution prepared in the step (2), stirring and reacting for 1.5h, and hydrolyzing to obtain 3, 3-trifluoropropanol;
(4) After the hydrolysis reaction is completed, the product is rectified to obtain 3, 3-trifluoro propanol, and the yield is calculated by weighing.
Example 8
The method specifically comprises the following steps:
(1) Drying a reaction kettle provided with a sealing stirrer, a cooling pipe, a constant-pressure dropping funnel and a reflux condenser, adding 1.1mol of magnesium powder, 500ml of polar solvent (the volume ratio of the polar solvent is tetrahydrofuran: toluene: N-methylmorpholine=8:1:1) and 0.5mol of bromoethane into the reaction kettle under the protection of nitrogen, dropwise adding 1mol of chlorotrifluoroethane and 500ml of polar solvent (the volume ratio of the polar solvent is tetrahydrofuran: toluene: N-methylmorpholine=8:1:1) into the reaction kettle, stirring and refluxing for 2 hours at 20 ℃ and 0.1MPa, and preparing a Grignard reagent CF 3CH2 MgCl solution;
(2) Dropwise adding 1mol of mixed solution of formaldehyde and a polar solvent into the mixed solution of the Grignard reagent CF 3CH2 MgCl prepared in the step (1) by using a constant pressure dropping funnel, wherein the dropwise adding rate is 5ml/min, and stirring and refluxing at 40 ℃ and 0.05MPa for 2h, and the stirring rate is 100r/min to prepare a CF 3CH2CH2 OMgCl solution;
(3) Adding 2mol of hydrochloric acid into the CF 3CH2CH2 OMgCl solution prepared in the step (2), stirring and reacting for 1.5h, and hydrolyzing to obtain 3, 3-trifluoropropanol;
(4) After the hydrolysis reaction is completed, the product is rectified to obtain 3, 3-trifluoro propanol, and the yield is calculated by weighing.
Example 9
The method specifically comprises the following steps:
(1) Drying a reaction kettle provided with a sealing stirrer, a cooling pipe, a constant-pressure dropping funnel and a reflux condenser, adding 1.1mol of magnesium powder, 500ml of polar solvent (the volume ratio of the polar solvent is tetrahydrofuran: toluene: N-methylmorpholine=8:1:1) and 0.5mol of ethyl orthosilicate into the reaction kettle under the protection of nitrogen, dropwise adding 1mol of chlorotrifluoroethane and 500ml of polar solvent (the volume ratio of the polar solvent is tetrahydrofuran: toluene: N-methylmorpholine=8:1:1) into the reaction kettle, stirring and refluxing for 2 hours at 30 ℃ and 0.1MPa, and preparing a Grignard reagent CF 3CH2 MgCl solution;
(2) Dropwise adding 1mol of mixed solution of formaldehyde and a polar solvent into the mixed solution of the Grignard reagent CF 3CH2 MgCl prepared in the step (1) by using a constant pressure dropping funnel, wherein the dropwise adding rate is 5ml/min, and stirring and refluxing at 20 ℃ and 0.1MPa for 2h, and the stirring rate is 100r/min to prepare a CF 3CH2CH2 OMgCl solution;
(3) Adding 2mol of hydrochloric acid into the CF 3CH2CH2 OMgCl solution prepared in the step (2), stirring and reacting for 1.5h, and hydrolyzing to obtain 3, 3-trifluoropropanol;
(4) After the hydrolysis reaction is completed, the product is rectified to obtain 3, 3-trifluoro propanol, and the yield is calculated by weighing.
Comparative example 1
The conditions for the step (1) of comparative example 1, 1-trifluorotrichloroethane, the other steps and the amounts of the respective substances were the same as those in example 1.
Comparative example 2
The conditions of the metallic zinc used in step (1) of comparative example 2, the other steps and the amounts of the respective substances are the same as those in example 1.
Comparative example 3
The conditions of the n-butyraldehyde used in step (2) of comparative example 3, the other steps and the amounts of the respective substances are the same as those in example 1.
Comparative example 4
The initiator used in step (1) of comparative example 4 was azobisisobutyronitrile, and the other conditions, such as the amounts of each of the other steps and each of the substances, were the same as those in example 1.
Comparative example 5
The polar solvent in comparative example 5 was composed of tetrahydrofuran and N, N-dimethylformamide in a volume ratio of 8:2, and the conditions of the other steps and the amounts of the substances were the same as those in example 1.
Comparative example 6
The volume ratio of the polar solvent in comparative example 6 is tetrahydrofuran: toluene: n-methylmorpholine=3:1:3, and the conditions of the other steps and the amounts of the respective substances are the same as in example 1.
Comparative example 7
In comparative example 7, the reflux reaction was carried out with stirring in the step (2) for 3.5 hours at a reaction temperature of 90℃under the same conditions as in example 1 except for the use amount of each of the other steps.
Comparative example 8
The reaction temperature in step (1) in comparative example 8 was 80℃and the conditions of the other steps, the amounts of the respective substances and the like were the same as those in example 1.
Example 10 calculation of 3, 3-trifluoropropanol yield
The final products of examples 1-9 and comparative examples 1-8 were weighed to calculate the yields, and the results are shown in Table 1.
Table 1 experimental characterization results for examples and comparative examples
The results show that the yields of the final 3, 3-trifluoropropanol of examples 1-9 using the preparation method defined in the application are all above 85%, wherein the yields of examples 7-9 are all above 90%, and a synthetic route with high yields of 3, 3-trifluoropropanol and mild reaction conditions is realized.
The 1, 1-trifluorotrichloroethane employed in step (1) of comparative example 1 was difficult to initiate the reaction, and the final hydrolysis produced 2, 2-dichloro-3, 3-trifluoropropanol with a final yield of 0.
The metallic zinc adopted in step (1) in comparative example 2, which is not a grignard reagent and is difficult to initiate reaction, cannot realize nucleophilic addition reaction of formaldehyde in the subsequent step, cannot hydrolyze to generate 3, 3-trifluoropropanol, and finally has a yield of 0.
Comparative example 3 the n-butyraldehyde employed in step (2) was a product of a secondary alcohol structure obtained by the nucleophilic addition reaction, and was not 3, 3-trifluoropropanol, but the final yield of 3, 3-trifluoropropanol was 0.
The initiator used in step (1) in comparative example 4 was azobisisobutyronitrile, which resulted in difficult initiation of the reaction in step (1), less CF 3CH2 MgCl was produced, and the final yield of 3, 3-trifluoropropanol was 34.8%, which was very low.
The composition of the polar solvent in comparative example 5 is tetrahydrofuran and N, N-dimethylformamide, the volume ratio of the tetrahydrofuran to the N, N-dimethylformamide is 8:2, the polar solvent can influence the initiation of the reaction and the generation of the product, and the yield of the final 3, 3-trifluoropropanol is 46.6 percent, and is lower.
The volume ratio of the polar solvent in comparative example 6 is tetrahydrofuran: toluene: n-methylmorpholine=3:1:3, the ratio of tetrahydrofuran to N-methylmorpholine is low, the nucleophilic reaction is insufficient, and the final yield of 3, 3-trifluoropropanol is 51.7%, which is low.
In the step (2) of the comparative example 7, the reaction temperature is 90 ℃ and the reaction time is long, and the reaction temperature is high, so that the generated CF 3CH2CH2 OMgCl is partially decomposed, and the final yield of the 3, 3-trifluoropropanol is 54.2%, and is low.
The reaction temperature in the step (1) in the comparative example 8 is 80 ℃, the temperature is higher, the prepared Grignard reagent CF 3CH2 MgCl solution is unstable, the final yield is 61.1%, and the yield is not high.
In summary, the preparation method of the 3, 3-trifluoropropanol uses the chlorotrifluoroethane as a raw material, uses Grignard reagents for nucleophilic reaction and hydrolysis reaction, and limits various reaction substances and conditions to prepare the 3, 3-trifluoropropanol, so that the preparation method is safe in process, mild in reaction conditions, high in yield of the 3, 3-trifluoropropanol, less in byproducts, recyclable in solvent, low in preparation raw material cost and easy to obtain.
The above is only an example of the present application, and the protective scope of the present application is not limited by the specific examples, but is defined by the claims of the present application. Various modifications and variations of the present application will be apparent to those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the technical idea and principle of the present application should be included in the protection scope of the present application.
Claims (4)
1. A method for preparing 3, 3-trifluoropropanol, which is characterized by comprising the following steps:
(1) Adding magnesium, a polar solvent and an initiator into a reaction container under the protection of nitrogen, dropwise adding a mixed solution of chlorotrifluoroethane and the polar solvent into the reaction container, stirring and refluxing for reaction for 1-3h, and preparing a Grignard reagent CF 3CH2 MgCl solution;
(2) Dropwise adding the mixed solution of formaldehyde and a polar solvent into the prepared mixed solution of the Grignard reagent CF 3CH2 MgCl, and stirring and refluxing for reaction for 1-2h to prepare a CF 3CH2CH2 OMgCl solution;
(3) Adding an acidic solution into the prepared CF 3CH2CH2 OMgCl solution, stirring and reacting for 1-2h, and hydrolyzing to obtain 3, 3-trifluoropropanol;
The reaction temperature of stirring reflux in the step (1) is 10-30 ℃, and the reaction pressure is 0-0.2MPa;
In the step (2), the reaction temperature of stirring reflux is 20-50 ℃ and the reaction pressure is 0-0.1MPa;
The polar solvent consists of tetrahydrofuran, toluene and N-methylmorpholine, wherein the volume ratio of the tetrahydrofuran to the toluene is (6-8): 1-2;
the initiator is at least one or more of iodine, bromine, methyl iodide, bromoethane, dibromoethane and ethyl orthosilicate.
2. The method according to claim 1, wherein the polar solvent in step (1) has a mass 3 to 20 times that of the chlorotrifluoroethane.
3. The method according to claim 1, wherein the polar solvent in step (2) has a mass of 0.5 to 5 times that of the formaldehyde.
4. The method according to claim 3, wherein the acidic solution is at least one or more of hydrochloric acid, sulfuric acid, nitric acid, acetic acid and formic acid.
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