CN107129511A - Preparation method and purposes containing an alkyl triphenyl phosphonium substituent quaternary alkylphosphonium salts - Google Patents
Preparation method and purposes containing an alkyl triphenyl phosphonium substituent quaternary alkylphosphonium salts Download PDFInfo
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- CN107129511A CN107129511A CN201610114857.5A CN201610114857A CN107129511A CN 107129511 A CN107129511 A CN 107129511A CN 201610114857 A CN201610114857 A CN 201610114857A CN 107129511 A CN107129511 A CN 107129511A
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- quaternary alkylphosphonium
- triphenyl phosphonium
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- 150000003839 salts Chemical class 0.000 title claims abstract description 56
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 238000006243 chemical reaction Methods 0.000 claims abstract description 40
- -1 alkyl triphenyl phosphonium Chemical compound 0.000 claims abstract description 36
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims abstract description 22
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims abstract description 18
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000006073 displacement reaction Methods 0.000 claims abstract description 9
- 230000000694 effects Effects 0.000 claims abstract description 8
- 239000002904 solvent Substances 0.000 claims abstract description 8
- 239000007864 aqueous solution Substances 0.000 claims abstract description 5
- 238000001953 recrystallisation Methods 0.000 claims abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 26
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 24
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 24
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 21
- 239000003054 catalyst Substances 0.000 claims description 19
- 239000007787 solid Substances 0.000 claims description 14
- 238000001514 detection method Methods 0.000 claims description 13
- 229910052757 nitrogen Inorganic materials 0.000 claims description 13
- 239000000047 product Substances 0.000 claims description 10
- 238000000967 suction filtration Methods 0.000 claims description 10
- 239000007789 gas Substances 0.000 claims description 9
- WFQDTOYDVUWQMS-UHFFFAOYSA-N 1-fluoro-4-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=C(F)C=C1 WFQDTOYDVUWQMS-UHFFFAOYSA-N 0.000 claims description 8
- 239000000706 filtrate Substances 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 238000001291 vacuum drying Methods 0.000 claims description 8
- 125000000217 alkyl group Chemical group 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 5
- 101710134784 Agnoprotein Proteins 0.000 claims description 4
- 241000220317 Rosa Species 0.000 claims description 4
- 238000004440 column chromatography Methods 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 239000012046 mixed solvent Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 150000002825 nitriles Chemical class 0.000 claims description 4
- 238000001556 precipitation Methods 0.000 claims description 4
- 238000010792 warming Methods 0.000 claims description 4
- RDHPKYGYEGBMSE-UHFFFAOYSA-N bromoethane Chemical compound CCBr RDHPKYGYEGBMSE-UHFFFAOYSA-N 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 229910001495 sodium tetrafluoroborate Inorganic materials 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 2
- 239000000843 powder Substances 0.000 claims description 2
- 125000001424 substituent group Chemical group 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- 239000003444 phase transfer catalyst Substances 0.000 abstract description 12
- 230000003197 catalytic effect Effects 0.000 abstract description 11
- 229910052731 fluorine Inorganic materials 0.000 abstract description 11
- 239000011737 fluorine Substances 0.000 abstract description 9
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 abstract description 7
- 230000000269 nucleophilic effect Effects 0.000 abstract description 6
- 230000001988 toxicity Effects 0.000 abstract description 5
- 231100000419 toxicity Toxicity 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 abstract description 4
- 239000000243 solution Substances 0.000 abstract description 3
- CZCSLHYZEQSUNV-UHFFFAOYSA-N [Na].OB(O)O Chemical compound [Na].OB(O)O CZCSLHYZEQSUNV-UHFFFAOYSA-N 0.000 abstract 1
- 150000001875 compounds Chemical class 0.000 abstract 1
- 150000004820 halides Chemical class 0.000 abstract 1
- 229930195733 hydrocarbon Natural products 0.000 abstract 1
- 238000005342 ion exchange Methods 0.000 abstract 1
- 238000004458 analytical method Methods 0.000 description 10
- 150000003983 crown ethers Chemical class 0.000 description 9
- HEDRZPFGACZZDS-MICDWDOJSA-N deuterated chloroform Substances [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 9
- HXELGNKCCDGMMN-UHFFFAOYSA-N [F].[Cl] Chemical compound [F].[Cl] HXELGNKCCDGMMN-UHFFFAOYSA-N 0.000 description 6
- 230000008901 benefit Effects 0.000 description 6
- 238000003682 fluorination reaction Methods 0.000 description 6
- XYFCBTPGUUZFHI-UHFFFAOYSA-N phosphine group Chemical group P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 6
- 229920000570 polyether Polymers 0.000 description 6
- 238000005160 1H NMR spectroscopy Methods 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 229910052801 chlorine Inorganic materials 0.000 description 4
- 239000000460 chlorine Substances 0.000 description 4
- 125000001153 fluoro group Chemical group F* 0.000 description 4
- 229910052736 halogen Inorganic materials 0.000 description 4
- 150000002367 halogens Chemical group 0.000 description 4
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 3
- 239000012074 organic phase Substances 0.000 description 3
- 125000004437 phosphorous atom Chemical group 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 239000008346 aqueous phase Substances 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 150000008282 halocarbons Chemical class 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 2
- 239000002798 polar solvent Substances 0.000 description 2
- 230000008092 positive effect Effects 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- FPGGTKZVZWFYPV-UHFFFAOYSA-M tetrabutylammonium fluoride Chemical compound [F-].CCCC[N+](CCCC)(CCCC)CCCC FPGGTKZVZWFYPV-UHFFFAOYSA-M 0.000 description 2
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 description 1
- CZGCEKJOLUNIFY-UHFFFAOYSA-N 4-Chloronitrobenzene Chemical compound [O-][N+](=O)C1=CC=C(Cl)C=C1 CZGCEKJOLUNIFY-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 229910020808 NaBF Inorganic materials 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 238000009841 combustion method Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010812 external standard method Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 150000003003 phosphines Chemical group 0.000 description 1
- 150000004714 phosphonium salts Chemical class 0.000 description 1
- 150000005375 primary alkyl halides Chemical class 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000000844 transformation Methods 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
- C07C201/06—Preparation of nitro compounds
- C07C201/12—Preparation of nitro compounds by reactions not involving the formation of nitro groups
-
- 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
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/54—Quaternary phosphonium compounds
- C07F9/5456—Arylalkanephosphonium compounds
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Catalysts (AREA)
Abstract
The present invention discloses a kind of preparation method and purposes for containing an alkyl triphenyl phosphonium substituent quaternary alkylphosphonium salts.Its preparation method is that the aqueous solution for obtaining alkyl triphenyl phosphonium quaternary alkylphosphonium salt a halide I, compound I by the reaction of nucleophilic displacement of fluorine in DMF solvent by several halogenated alkyl hydrocarbons and triphenylphosphine is made in high yield with tetrafluoro boric acid sodium water solution by ion exchange by recrystallization again.The present invention has raw material cheap and easy to get and prepares the characteristics of cost is low, have catalytic activity high, few dosage that are needing, activity time length, heat endurance high when the prepared quaternary alkylphosphonium salt II containing an alkyl triphenyl phosphonium substituent is as Catalyzed By Phase-transfer Catalyst exchange chloride for fluoride and the features such as toxicity is low, reaction yield is high, industrial applications prospect is wide.
Description
Technical field
The invention belongs to quaternary phosphine phase transfer catalyst technical field.It is specifically related to a kind of to contain an alkyl triphenyl phosphonium substituent quaternary phosphines
The preparation method and purposes of salt.
Background technology
C-F keys are all widely used in pharmacy, agricultural chemicals, new material and biological field.Because fluorine atom electronegativity is high, atom half
Footpath is small, to introduce fluorine atom difficulty in organic matter ad-hoc location very big.Halogen-exchange fluorination method is industrial at present most widely used, is ground
Study carefully most popular fluorination process, phase transfer catalyst is the key of halogen-exchange fluorination method development, crown ether, polyethers, quaternary ammonium salt and season
Phosphonium salt catalyst is four dominant catalysts of halogen-exchange fluorination method.
Crown ether and chain ether catalyst are using PTC earlier, by coordinating with alkali metal cation formation in halogen exchange reaction
Thing, forms " naked " F-The characteristics of ion, crown ether is that catalytic activity is high, and heat endurance and chemical stability are good but expensive,
Toxicity is big, and main and other catalyst interworkings are used in halogen exchange reaction;Polyethers (such as PEG) cheap, small toxicity,
Chemical stability is good, and frequently as the alternative catalysts of crown ether and quaternary ammonium salt, but heat endurance is poor, Ji Woong Lee,
(Ji Woong Lee, Hailong Yan, Hyeong Bin Jang, the Hong Ki Kim.Bis-Terminal such as Hailong Yan
Hydroxy Polyethers as All-Purpose, Multifunctional Organic Promoters:A Mechanistic Investigation
And Applications.Angew.Chew.Int.Ed.2009,48:7683-7686.) by crown ether and Crown ether application in exchange chloride for fluoride
In, product yield only up to 40%;Quaternary ammonium salt catalytic activity is high, but heat endurance is poor, starts when temperature is more than 100 DEG C point
Solution, easily produces (Dong the Wook Kim, Hwan-Jeong such as accessory substance Dong Wook Kim, Hwan-Jeong Jeong
Jeong, Seok Tae Lim, Myung-Hee Sohn.Facile nucleophilic fluorination of primary alkyl halides
Using tetrabutylammonium fluoride in a tert-alcohol medium.Tetrahedron Letters 2010,51:432-434.)
Quaternary ammonium salt is applied in exchange chloride for fluoride, obtained product yield is also only 56%.Polyethers, crown ether catalytic mechanism are to pass through
Increase KF reactivity, and this raising reactivity is more than due to improving solubility of the KF in organic phase, more may be used
It can be due to that it destroys KF crystalline structures, discharge F-Ion;Quaternary salt catalytic mechanism belongs to the steady of increase mediating complex
It is qualitative.
Due to having three unpaired electrons, a pair of lone pair electrons and 5 sky 3d tracks on phosphorus atoms, make Ph3P+Possess suction electrical,
Cause quaternary phosphine salt cation and F again-Have good binding ability, be conducive to the progress of fluorination reaction, due to its excellent catalytic effect,
Selectivity height, heat endurance height, small toxicity, can be recycled, quaternary phosphine phase transfer catalyst is used widely in recent years.
The content of the invention
It is contemplated that overcoming prior art defect, it is therefore an objective to provide a kind of raw material it is cheap and easy to get and prepare cost it is low contain an alkyl
The preparation method of triphenyl substituent quaternary alkylphosphonium salts;What is prepared with this method contains an alkyl triphenyl phosphonium substituent quaternary alkylphosphonium salt II conducts
Have high catalytic activity, few activation dosage that is needing, activity time length, heat steady during Catalyzed By Phase-transfer Catalyst exchange chloride for fluoride
Qualitative high and toxicity is low, exchange chloride for fluoride high income the features such as, industrial applications prospect is wide.
To achieve the above object, the technical solution adopted by the present invention is:The alkyl triphenyl phosphonium substituent quaternary alkylphosphonium salts that contain are designated as
II, its structural formula is:
Wherein:R is alkyl.
Preparation method containing an alkyl triphenyl phosphonium substituent quaternary alkylphosphonium salts II is comprised the concrete steps that:
Step 1: quaternary alkylphosphonium salt halide I preparation
Quaternary alkylphosphonium salt halide I structural formula is:
Wherein:R is alkyl;
Quaternary alkylphosphonium salt halide I preparation:7.86g (0.03mol) triphenylphosphines and 20ml acetonitriles are added equipped with condenser pipe
In 100ml three-necked flasks, lower constant pressure dropping 6mL (0.06mol) bromoethane of nitrogen protection, return stirring reaction 10h, reaction
After finishing, homogeneous yellow oily liquid is obtained, refrigerator cooling is placed in, after white solid is separated out, filters out white solid, use second
Nitrile and ethyl acetate mixture recrystallization, then suction filtration is depressurized, dried in 60 DEG C of vacuum drying chambers, obtain white solid as season
Phosphonium salt halide I.
The volume ratio of the acetonitrile: ethyl acetate of the in the mixed solvent is 1: 2;
Step 2: the preparation containing an alkyl triphenyl phosphonium substituent quaternary alkylphosphonium salts II
Quaternary alkylphosphonium salt halide I described in 0.03mol is dissolved in 50mL water, under the conditions of 60 DEG C heating stirring until be completely dissolved,
Add excessive NaBF4There is White Flocculus at once in the aqueous solution, reaction system, and continuation is stirred 12h, taken out at ambient temperature
White solid, washed reaction thing are filtered to obtain, until adding AgNO in filtrate3No longer occur after precipitation, with recrystallized from acetonitrile, then depressurize
Suction filtration, is dried in 60 DEG C of vacuum drying chambers, and it is to contain an alkyl triphenyl phosphonium substituent quaternary alkylphosphonium salt II to obtain white powder, by institute
State containing an alkyl triphenyl phosphonium substituent quaternary alkylphosphonium salts II as be detected in drying box.
Purposes containing an alkyl triphenyl phosphonium substituent quaternary alkylphosphonium salts II, the quaternary alkylphosphonium salts are used to be catalyzed fluorine as phase transfer catalyst
Chlorine exchange reaction, is comprised the concrete steps that:
Step 1: take a certain amount of SD-KF to be fitted into crucible carries out fire in Muffle furnace, temperature gradually rose and every half an hour
Once ground, continue to dry 15h until Muffle furnace is warming up to after 600 DEG C, then after the dry 3h of 150 DEG C of vacuum dried case
It is standby;
Step 2: 1.2g SD-KF, the 0.03g just pre-processed is put into the 100mL three-necked flasks for be connected to condenser pipe contains one
Alkyl triphenyl phosphonium substituent quaternary alkylphosphonium salts, 1.6g parachloronitrobenzenes, 20mLDMSO, the air gone out with nitrogen displacement in reaction bulb,
Back flow reaction 6h under nitrogen protection is added, is sampled once per hour, gas chromatographic detection is carried out;
Step 3: releasing material from reactor, filter, obtain filtrate, solvent DMSO is evaporated off, then separate through col-umn chromatography
Obtain product p-fluoronitrobenzene;
Step 4: weighing products therefrom, calculated yield, by gas chromatographic detection figure, contains an alkyl triphen by yield reaction
Base substituent quaternary alkylphosphonium salts II as the catalyst of exchange chloride for fluoride activity.
Due to using above-mentioned technical proposal, the present invention has the positive effect that compared with prior art:
Due to the quaternary phosphine salt cation [Ph in quaternary alkylphosphonium salt II3PR]+With F-There is good binding ability, so, catalyst cation is not
Fluorine ion is extracted into organic phase reaction center by boundary and reaction is constantly efficiently gone on by coming and going for stopping, thus is adopted
The catalysis fluorine chlorine containing an alkyl triphenyl phosphonium substituent quaternary alkylphosphonium salts II prepared with the present invention has agent consumption few and catalytic activity when exchanging
High advantage.
Due to having three unpaired electrons, a pair of lone pair electrons and 5 sky 3d on the P atoms in quaternary alkylphosphonium salt halide I molecules
Track, makes Ph3P+Possess suction electrical, it is had larger bond energy when larger atom of electronegativity is combined with halogen etc., thus make it
Further can occur nucleophilic displacement of fluorine substitution reaction with halogenated hydrocarbons, form highly stable active centre, such catalyst system and catalyzing is by fluorine
The influence that chlorine exchanges side reaction is smaller.Such catalyst can efficiently extract and be dissolved in micro- aqueous phase the long period in polar solvent
Fluorine ion, accelerates the progress of reaction so that this kind of catalyst has bigger in exchange chloride for fluoride than common phase transfer catalyst
Application prospect.
Because quaternary alkylphosphonium salt halide I is made in high yield using triphenylphosphine and halogenated alkane cheap and easy to get by nucleophilic displacement of fluorine,
Therefore, the quaternary alkylphosphonium salt halide I costs of the gained catalyst expensive far below synthesizing polyether, crown ether etc., with preparing, cost is low
Advantage.
Because common phase transfer catalyst heat endurance is relatively low, and exchange chloride for fluoride needs to carry out under the high temperature conditions.
Comparatively, the present invention prepare containing an alkyl triphenyl phosphonium substituent quaternary alkylphosphonium salts II in DMSO solvents in higher temperature model
The exchange of fluorine chlorine, thus more advantage can be catalyzed by enclosing (160-200 DEG C).
Therefore, the present invention has raw material cheap and easy to get and prepares the characteristics of cost is low, and prepared contains an alkyl triphenyl phosphonium substituent
Catalytic activity height, few dosage needed, activity time length, heat endurance are high and malicious when quaternary alkylphosphonium salts II is catalyzed exchange chloride for fluoride
The features such as property is low, reaction yield is high, industrial applications prospect is wide.
Brief description of the drawings
Fig. 1 a kind of contains an alkyl triphenyl phosphonium substituent quaternary alkylphosphonium salts II for prepared by the present invention1Infrared spectrogram;
Fig. 2 is to contain an alkyl triphenyl phosphonium substituent quaternary alkylphosphonium salts II shown in Fig. 11Fluorine chlorine exchange system is catalyzed for the gas phase of p-fluoronitrobenzene
Chromatogram.
Embodiment
The invention will be further described with reference to the accompanying drawings and detailed description, not to the limitation of its protection domain.
The preparation of packet Kuo quaternary alkylphosphonium salt halide I He quaternary alkylphosphonium salt II given by present embodiment are exchanged with sign, fluorine chlorine
Operation, condition and the product of reaction.Quaternary alkylphosphonium salt halide I is He quaternary alkylphosphonium salt II1H-NMR uses BrukerAvance DMX
400 NMRs, using CDCl3Make solvent, TMS is used as internal standard;Elementary analysis is in Perkin Elmer240 elementary analyses
Carried out on instrument, using quantitative oxygen combustion method, detector is made with conductance cell;Infrared spectrum uses the type Fourier transformations of Uertex 70
Infrared spectrometer, KBr tablettings.Fluorine chlorine exchanges product and carries out quantitative and qualitative detection, GC analysis conditions using GC-External Standard method
For using high pure nitrogen as carrier gas, flow velocity is 1.2ml/min;300 DEG C of temperature of vaporization chamber, temperature programming:80 DEG C of initial temperature, is pressed
15 DEG C/min rises to 300 DEG C, 300 DEG C of column temperature;Split ratio 50: 1;The μ L of sample size 1.Appearance time:10.544min(DMSO)、
14.053min (p-fluoronitrobenzene), 16.768min (parachloronitrobenzene).
Embodiment 1
It is a kind of to contain alkyl triphenyl phosphonium substituent quaternary alkylphosphonium salts and preparation method thereof.It is described to contain an alkyl triphenyl phosphonium substituent quaternary phosphines
Salt is designated as II1, its structural formula is:
II is designated as containing many alkyl triphenyl phosphonium substituent quaternary alkylphosphonium salts1Preparation method comprise the concrete steps that:
Step 1: quaternary alkylphosphonium salt halide I1Preparation
Quaternary alkylphosphonium salt halide I1Structural formula be:
Quaternary alkylphosphonium salt halide I1Preparation:7.86g (0.03mol) triphenylphosphines and 20ml acetonitriles are added equipped with condenser pipe
In 100ml three-necked flasks, lower constant pressure dropping 6mL (0.06mol) bromoethane of nitrogen protection, return stirring reaction 10h, reaction
After finishing, homogeneous yellow oily liquid is obtained, refrigerator cooling is placed in, after white solid is separated out, filters out white solid, use second
Nitrile and ethyl acetate mixture recrystallization, then suction filtration is depressurized, dried in 60 DEG C of vacuum drying chambers, obtain 8.16g (0.025mol)
Quaternary alkylphosphonium salt halide I1, molar yield is 83.2%.
The volume ratio of the acetonitrile: ethyl acetate of the in the mixed solvent is 1: 2;
Quaternary alkylphosphonium salt halide I1Relevant detection and analysis data it is as follows:
Elementary analysis:I1(C20H20PCl, 326.5g/mol) measured value (theoretical value):C is 73.89% (73.51%), and H is
6.10% (6.13%);1HNMR (600MHz, CDCl3) δ 7.91~7.51 (m, 15H), 3.95 (q, J=7.3Hz, 2H),
1.40 (t, J=7.4Hz, 3H);IR (KBr), v, cm-1:2900,1432,1110,751,692,535,497.
Step 2: containing an alkyl triphenyl phosphonium substituent quaternary alkylphosphonium salts II1Preparation
By 9.80g (0.03mol) the quaternary alkylphosphonium salt halide I1Be dissolved in 50mL water, under the conditions of 60 DEG C heating stirring until
It is completely dissolved, adds excessive NaBF4There is White Flocculus at once in the aqueous solution, reaction system, and continuation is stirred at ambient temperature
12h is mixed, suction filtration obtains white solid, washed reaction thing, until adding AgNO in filtrate3No longer occur after precipitation, tied again with acetonitrile
Crystalline substance, then suction filtration is depressurized, dried in 60 DEG C of vacuum drying chambers, obtain 8.31g (0.022mol) and contain an alkyl triphenyl phosphonium substituent
Quaternary alkylphosphonium salt II1, molar yield is 73.33%.
Quaternary alkylphosphonium salt II1Relevant detection and analysis data are as follows:
Elementary analysis:II1(C20H20PBF4, 377.8g/mol) and measured value (theoretical value):C is 63.49% (63.52%), and H is
5.31% (5.29%);1HNMR (600MHz, CDCl3) δ 7.84~7.51 (m, 15H), 3.42 (q, J=7.8Hz, 2H),
1.39 (t, J=7.4Hz, 3H);IR (KBr), v, cm-1:2894,1438,1116,742,690,515,497.
Embodiment 2
It is a kind of to contain an alkyl triphenyl phosphonium substituent quaternary alkylphosphonium salts II1Purposes.The quaternary alkylphosphonium salts II1Used as phase transfer catalyst
In exchange chloride for fluoride, comprise the concrete steps that:
Step 1: take a certain amount of SD-KF to be fitted into crucible carries out fire in Muffle furnace, temperature gradually rose and every half an hour
Once ground, continue to dry 15h until Muffle furnace is warming up to after 600 DEG C, then after the dry 3h of 150 DEG C of vacuum dried case
It is standby;
Step 2: 1.2g SD-KF, the 0.03g just pre-processed is put into the 100mL three-necked flasks for be connected to condenser pipe contains one
Alkyl triphenyl phosphonium substituent quaternary alkylphosphonium salts II1, 1.6g parachloronitrobenzenes, 20mLDMSO, gone out with nitrogen displacement in reaction bulb
Air, adds back flow reaction 6h under nitrogen protection, is sampled once per hour, and carries out gas chromatographic detection;
Step 3: releasing material from reactor, filter, obtain filtrate, solvent DMSO is evaporated off, then separate through col-umn chromatography
Obtain product p-fluoronitrobenzene;
Step 4: it is 82.87% to calculate the yield of p-fluoronitrobenzene by gas chromatographic detection figure, contained by the high low reaction of yield
One alkyl triphenyl phosphonium substituent quaternary alkylphosphonium salts II1It is used as the activity of the catalyst of exchange chloride for fluoride.
Embodiment 3
It is a kind of to contain alkyl triphenyl phosphonium substituent quaternary alkylphosphonium salts and preparation method thereof.It is described to contain an alkyl triphenyl phosphonium substituent quaternary phosphines
Salt is designated as II2, its structural formula is:
II is designated as containing many alkyl triphenyl phosphonium substituent quaternary alkylphosphonium salts2Preparation method comprise the concrete steps that:
Step 1: quaternary alkylphosphonium salt halide I2Preparation
Quaternary alkylphosphonium salt halide I2Structural formula be:
Quaternary alkylphosphonium salt halide I2Preparation:7.86g (0.03mol) triphenylphosphines and 20ml acetonitriles are added equipped with condenser pipe
In 100ml three-necked flasks, lower constant pressure dropping 8mL (0.06mol) NBB of nitrogen protection, return stirring reaction 10h, reaction
After finishing, homogeneous yellow oily liquid is obtained, refrigerator cooling is placed in, after white solid is separated out, filters out white solid, use second
Nitrile and ethyl acetate mixture recrystallization, then suction filtration is depressurized, dried in 60 DEG C of vacuum drying chambers, obtain 9.22g (0.026mol)
Quaternary alkylphosphonium salt halide I2, molar yield is 86.7%.
The volume ratio of the acetonitrile: ethyl acetate of the in the mixed solvent is 1: 2;
Quaternary alkylphosphonium salt halide I2Relevant detection and analysis data it is as follows:
Elementary analysis:I2(C22H24PCl, 354.5g/mol) measured value (theoretical value):C is 74.39% (74.47%), and H is
6.70% (6.77%);1HNMR (600MHz, CDCl3) δ 7.90~7.69 (m, 15H), 3.85 (t, J=14.8Hz, 2H),
1.69 (m, 2H), 1.59 (dt, J=15.3,7.1Hz, 2H), 0.90 (t, J=7.3Hz, 3H);IR (KBr), v, cm-1:
2879,1434,1107,752,681,532,497.
Step 2: containing an alkyl triphenyl phosphonium substituent quaternary alkylphosphonium salts II2Preparation
By 10.64g (0.03mol) the quaternary alkylphosphonium salt halide I2It is dissolved in 50mL water, heating stirring is straight under the conditions of 60 DEG C
To being completely dissolved, excessive NaBF is added4There is White Flocculus at once in the aqueous solution, reaction system, continues at ambient temperature
12h is stirred, suction filtration obtains white solid, washed reaction thing, until adding AgNO in filtrate3No longer occur after precipitation, use acetonitrile weight
Crystallization, then suction filtration is depressurized, dried in 60 DEG C of vacuum drying chambers, obtain 9.33g (0.023mol) containing an alkyl triphenyl phosphonium substituent
Quaternary alkylphosphonium salts II2, molar yield is 76.67%.
Quaternary alkylphosphonium salt II2Relevant detection and analysis data are as follows:
Elementary analysis:II2(C22H24PBF4, 405.8g/mol) and measured value (theoretical value):C is 65.49% (65.05%), and H is
5.93% (5.91%);1HNMR (600MHz, CDCl3) δ 7.82~7.70 (m, 15H), 3.31 (t, J=14.2Hz, 2H),
1.61 (m, 2H), 1.56 (dt, J=14.0,7.2Hz, 2H), 0.92 (t, J=7.0Hz, 3H);IR (KBr), v,
cm-1:2879,1438,1118,751,690,532,497.
Embodiment 4
It is a kind of to contain an alkyl triphenyl phosphonium substituent quaternary alkylphosphonium salts II2Purposes.The quaternary alkylphosphonium salts II2Used as phase transfer catalyst
In exchange chloride for fluoride, comprise the concrete steps that:
Step 1: take a certain amount of SD-KF to be fitted into crucible carries out fire in Muffle furnace, temperature gradually rose and every half an hour
Once ground, continue to dry 15h until Muffle furnace is warming up to after 600 DEG C, then after the dry 3h of 150 DEG C of vacuum dried case
It is standby;
Step 2: 1.2g SD-KF, the 0.03g just pre-processed is put into the 100mL three-necked flasks for be connected to condenser pipe contains one
Alkyl triphenyl phosphonium substituent quaternary alkylphosphonium salts II2, 1.6g parachloronitrobenzenes, 20mLDMSO, gone out with nitrogen displacement in reaction bulb
Air, adds back flow reaction 6h under nitrogen protection, is sampled once per hour, and carries out gas chromatographic detection;
Step 3: releasing material from reactor, filter, obtain filtrate, solvent DMSO is evaporated off, then separate through col-umn chromatography
Obtain product p-fluoronitrobenzene;
Step 4: it is 84.54% to calculate the yield of p-fluoronitrobenzene by gas chromatographic detection figure, contained by the high low reaction of yield
One alkyl triphenyl phosphonium substituent quaternary alkylphosphonium salts II2It is used as the activity of the catalyst of exchange chloride for fluoride.
Present embodiment has the positive effect that compared with prior art:
Due to the quaternary phosphine salt cation [Ph in quaternary alkylphosphonium salt II3PR]+With F-There is good binding ability, so, catalyst cation is not
Fluorine ion is extracted into organic phase reaction center by boundary and reaction is constantly efficiently gone on by coming and going for stopping, thus is adopted
The catalysis fluorine chlorine containing an alkyl triphenyl phosphonium substituent quaternary alkylphosphonium salts II prepared with the present invention has agent consumption few and catalytic activity when exchanging
High advantage.
Due to having three unpaired electrons, a pair of lone pair electrons and 5 sky 3d on the P atoms in quaternary alkylphosphonium salt halide I molecules
Track, makes Ph3P+Possess suction electrical, it is had larger bond energy when larger atom of electronegativity is combined with halogen etc., thus make it
Further can occur nucleophilic displacement of fluorine substitution reaction with halogenated hydrocarbons, form highly stable active centre, such catalyst system and catalyzing is by fluorine
The influence that chlorine exchanges side reaction is smaller.Such catalyst can efficiently extract and be dissolved in micro- aqueous phase the long period in polar solvent
Fluorine ion, accelerates the progress of reaction so that this kind of catalyst has bigger in exchange chloride for fluoride than common phase transfer catalyst
Application prospect.
Because quaternary alkylphosphonium salt halide I is made in high yield using triphenylphosphine and halogenated alkane cheap and easy to get by nucleophilic displacement of fluorine,
Therefore, the quaternary alkylphosphonium salt halide I costs of the gained catalyst expensive far below synthesizing polyether, crown ether etc., with preparing, cost is low
Advantage.
Because common phase transfer catalyst heat endurance is relatively low, and exchange chloride for fluoride needs to carry out under the high temperature conditions.
Comparatively, the present invention prepare containing an alkyl triphenyl phosphonium substituent quaternary alkylphosphonium salts II in DMSO solvents in higher temperature model
The exchange of fluorine chlorine, thus more advantage can be catalyzed by enclosing (160-200 DEG C).
Therefore, the present invention has raw material cheap and easy to get and prepares the characteristics of cost is low, and prepared contains an alkyl triphenyl phosphonium substituent
Catalytic activity height, few dosage needed, activity time length, heat endurance are high and malicious when quaternary alkylphosphonium salts II is catalyzed exchange chloride for fluoride
The features such as property is low, reaction yield is high, industrial applications prospect is wide.
Claims (3)
1. a kind of contain an alkyl triphenyl phosphonium substituent quaternary alkylphosphonium salts, it is characterised in that described to contain an alkyl triphenyl phosphonium substituent containing a kind of
Quaternary alkylphosphonium salts are designated as II, and its structural formula is:
Wherein:R is alkyl.
2. a kind of preparation method for containing an alkyl triphenyl phosphonium substituent quaternary alkylphosphonium salts, it is characterised in that the specific step of the preparation method
Suddenly it is:
Step 1: quaternary alkylphosphonium salt halide I preparation
Quaternary alkylphosphonium salt halide I structural formula is:
Wherein:R is alkyl;
Quaternary alkylphosphonium salt halide I preparation:7.86g (0.03mol) triphenylphosphines and 20ml acetonitriles are added equipped with condenser pipe
In 100ml three-necked flasks, lower constant pressure dropping 6mL (0.06mol) bromoethane of nitrogen protection, return stirring reaction 10h, reaction
After finishing, homogeneous yellow oily liquid is obtained, refrigerator cooling is placed in, after white solid is separated out, filters out white solid, use second
Nitrile and ethyl acetate mixture recrystallization, then suction filtration is depressurized, dried in 60 DEG C of vacuum drying chambers, obtain white solid as season
Phosphonium salt halide I;
The acetonitrile of the in the mixed solvent:The volume ratio of ethyl acetate is 1: 2;
Step 2: the preparation containing an alkyl triphenyl phosphonium substituent quaternary alkylphosphonium salts II
Quaternary alkylphosphonium salt halide I described in 0.03mol is dissolved in 50mL water, under the conditions of 60 DEG C heating stirring until be completely dissolved,
The excessive NaBF4 aqueous solution is added, White Flocculus occurs at once in reaction system, and continuation is stirred 12h, taken out at ambient temperature
White solid, washed reaction thing are filtered to obtain, until adding AgNO in filtrate3No longer occur after precipitation, with recrystallized from acetonitrile, then depressurize
Suction filtration, is dried in 60 DEG C of vacuum drying chambers, and it is to contain an alkyl triphenyl phosphonium substituent quaternary alkylphosphonium salt II to obtain white powder, by institute
State containing an alkyl triphenyl phosphonium substituent quaternary alkylphosphonium salts II as be detected in drying box.
3. a kind of purposes for containing an alkyl triphenyl phosphonium substituent quaternary alkylphosphonium salts, it is characterised in that the quaternary alkylphosphonium salts are urged as phase transfer
Agent is used to be catalyzed exchange chloride for fluoride, comprises the concrete steps that:
Step 1: take a certain amount of SD-KF to be fitted into crucible carries out fire in Muffle furnace, temperature gradually rose and every half an hour
Once ground, continue to dry 15h until Muffle furnace is warming up to after 600 DEG C, then after the dry 3h of 150 DEG C of vacuum dried case
It is standby;
Step 2: 1.2g SD-KF, the 0.03g just pre-processed is put into the 100mL three-necked flasks for be connected to condenser pipe contains one
Alkyl triphenyl phosphonium substituent quaternary alkylphosphonium salts, 1.6g parachloronitrobenzenes, 20mLDMSO, the air gone out with nitrogen displacement in reaction bulb,
Back flow reaction 6h under nitrogen protection is added, is sampled once per hour, gas chromatographic detection is carried out;
Step 3: releasing material from reactor, filter, obtain filtrate, solvent DMSO is evaporated off, then separate through col-umn chromatography
Obtain product p-fluoronitrobenzene;
Step 4: weighing products therefrom, calculated yield, by gas chromatographic detection figure, contains an alkyl triphen by yield reaction
Base substituent quaternary alkylphosphonium salts II as the catalyst of exchange chloride for fluoride activity.
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Cited By (2)
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CN108586257A (en) * | 2018-05-03 | 2018-09-28 | 浙江解氏新材料股份有限公司 | A kind of novel processing step of p-fluoronitrobenzene |
EP3696156A1 (en) | 2019-02-15 | 2020-08-19 | Fujian Yongjing Technology Co., Ltd. | New process for the manufacture of fluoroaryl compounds and derivatives |
-
2016
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Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
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CN108586257A (en) * | 2018-05-03 | 2018-09-28 | 浙江解氏新材料股份有限公司 | A kind of novel processing step of p-fluoronitrobenzene |
EP3696156A1 (en) | 2019-02-15 | 2020-08-19 | Fujian Yongjing Technology Co., Ltd. | New process for the manufacture of fluoroaryl compounds and derivatives |
WO2020164217A1 (en) * | 2019-02-15 | 2020-08-20 | Fujian Yongjing Technology Co., Ltd | New process for manufacture of fluoroaryl compounds and derivatives |
US11420917B2 (en) | 2019-02-15 | 2022-08-23 | Fujian Yongjing Technology Co., Ltd. | Process for the manufacture of fluoroaryl compounds and derivatives |
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