CN108676033A - The synthetic method of antimony triphenyl - Google Patents
The synthetic method of antimony triphenyl Download PDFInfo
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- CN108676033A CN108676033A CN201810808638.6A CN201810808638A CN108676033A CN 108676033 A CN108676033 A CN 108676033A CN 201810808638 A CN201810808638 A CN 201810808638A CN 108676033 A CN108676033 A CN 108676033A
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- China
- Prior art keywords
- antimony
- added dropwise
- triphenyl
- benzene
- antimony triphenyl
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- 229910052787 antimony Inorganic materials 0.000 title claims abstract description 70
- 238000010189 synthetic method Methods 0.000 title claims abstract description 25
- 238000006243 chemical reaction Methods 0.000 claims abstract description 54
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Substances C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims abstract description 40
- 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 claims abstract description 23
- 239000011261 inert gas Substances 0.000 claims abstract description 23
- 239000011734 sodium Substances 0.000 claims abstract description 23
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 23
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000000706 filtrate Substances 0.000 claims abstract description 22
- 239000012043 crude product Substances 0.000 claims abstract description 19
- DAMJCWMGELCIMI-UHFFFAOYSA-N benzyl n-(2-oxopyrrolidin-3-yl)carbamate Chemical compound C=1C=CC=CC=1COC(=O)NC1CCNC1=O DAMJCWMGELCIMI-UHFFFAOYSA-N 0.000 claims abstract description 16
- 235000014113 dietary fatty acids Nutrition 0.000 claims abstract description 16
- 229930195729 fatty acid Natural products 0.000 claims abstract description 16
- 239000000194 fatty acid Substances 0.000 claims abstract description 16
- 238000007710 freezing Methods 0.000 claims abstract description 11
- 230000008014 freezing Effects 0.000 claims abstract description 11
- 239000003960 organic solvent Substances 0.000 claims abstract description 11
- 239000003208 petroleum Substances 0.000 claims abstract description 11
- 150000004665 fatty acids Chemical class 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 9
- -1 fatty acid salt Chemical class 0.000 claims abstract description 8
- 238000004090 dissolution Methods 0.000 claims abstract description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Substances ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 54
- 238000003756 stirring Methods 0.000 claims description 30
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 23
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 claims description 22
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 13
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 9
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 8
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 8
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 8
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 8
- 239000005642 Oleic acid Substances 0.000 claims description 8
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 8
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 8
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 6
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 4
- 235000021355 Stearic acid Nutrition 0.000 claims description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 4
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 4
- 239000008117 stearic acid Substances 0.000 claims description 4
- WBIQQQGBSDOWNP-UHFFFAOYSA-N 2-dodecylbenzenesulfonic acid Chemical compound CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O WBIQQQGBSDOWNP-UHFFFAOYSA-N 0.000 claims description 2
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 2
- YCOXTKKNXUZSKD-UHFFFAOYSA-N as-o-xylenol Natural products CC1=CC=C(O)C=C1C YCOXTKKNXUZSKD-UHFFFAOYSA-N 0.000 claims description 2
- MVPPADPHJFYWMZ-IDEBNGHGSA-N chlorobenzene Chemical group Cl[13C]1=[13CH][13CH]=[13CH][13CH]=[13CH]1 MVPPADPHJFYWMZ-IDEBNGHGSA-N 0.000 claims description 2
- 229940060296 dodecylbenzenesulfonic acid Drugs 0.000 claims description 2
- SNHMUERNLJLMHN-UHFFFAOYSA-N iodobenzene Chemical compound IC1=CC=CC=C1 SNHMUERNLJLMHN-UHFFFAOYSA-N 0.000 claims description 2
- 150000002617 leukotrienes Chemical class 0.000 claims description 2
- ZDUWWYGMPBROEJ-UHFFFAOYSA-N phenylantimony Chemical compound [Sb]C1=CC=CC=C1 ZDUWWYGMPBROEJ-UHFFFAOYSA-N 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 125000003944 tolyl group Chemical group 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 4
- 238000001914 filtration Methods 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 239000000047 product Substances 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 4
- 239000002699 waste material Substances 0.000 abstract description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 48
- 239000000243 solution Substances 0.000 description 36
- 229910052757 nitrogen Inorganic materials 0.000 description 24
- 238000010792 warming Methods 0.000 description 16
- 239000002893 slag Substances 0.000 description 14
- 238000010992 reflux Methods 0.000 description 9
- 239000012141 concentrate Substances 0.000 description 7
- 239000013078 crystal Substances 0.000 description 7
- 238000004064 recycling Methods 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 4
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- FAPDDOBMIUGHIN-UHFFFAOYSA-K antimony trichloride Chemical class Cl[Sb](Cl)Cl FAPDDOBMIUGHIN-UHFFFAOYSA-K 0.000 description 2
- 235000010290 biphenyl Nutrition 0.000 description 2
- 239000004305 biphenyl Substances 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229920006389 polyphenyl polymer Polymers 0.000 description 2
- 239000010802 sludge Substances 0.000 description 2
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 2
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 239000007818 Grignard reagent Substances 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 235000006708 antioxidants Nutrition 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- SSXPEHBFLFUZCU-UHFFFAOYSA-M chloro(diphenyl)stibane Chemical compound C=1C=CC=CC=1[Sb](Cl)C1=CC=CC=C1 SSXPEHBFLFUZCU-UHFFFAOYSA-M 0.000 description 1
- 150000008422 chlorobenzenes Chemical class 0.000 description 1
- 208000012839 conversion disease Diseases 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 150000004795 grignard reagents Chemical class 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- ODZPKZBBUMBTMG-UHFFFAOYSA-N sodium amide Chemical compound [NH2-].[Na+] ODZPKZBBUMBTMG-UHFFFAOYSA-N 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- RYYKJJJTJZKILX-UHFFFAOYSA-M sodium octadecanoate Chemical class [Na+].CCCCCCCCCCCCCCCCCC([O-])=O RYYKJJJTJZKILX-UHFFFAOYSA-M 0.000 description 1
- KSMWLICLECSXMI-UHFFFAOYSA-N sodium;benzene Chemical compound [Na+].C1=CC=[C-]C=C1 KSMWLICLECSXMI-UHFFFAOYSA-N 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- SBXWFLISHPUINY-UHFFFAOYSA-N triphenyltin Chemical compound C1=CC=CC=C1[Sn](C=1C=CC=CC=1)C1=CC=CC=C1 SBXWFLISHPUINY-UHFFFAOYSA-N 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
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/90—Antimony compounds
- C07F9/92—Aromatic compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a kind of synthetic methods of antimony triphenyl, include the following steps：Under the protection of inert gas, higher fatty acids or higher fatty acid salt are added in organic solvent, and sodium, back flow reaction postcooling to room temperature is added；Halogeno-benzene is first slowly added dropwise into the solution of gained, then the halogenated benzole soln of antimony trichloride is slowly added dropwise and is stirred to react, the reaction solution filtering of gained is evaporated off organic solvent, halogeno-benzene under the filtrate normal pressure of gained, obtains antimony triphenyl crude product；By crude product petroleum ether dissolution, filtering, freezing and crystallizing after the filtrate concentration of gained obtains antimony triphenyl.Method using the present invention synthesizes antimony triphenyl, and raw material availability is high, avoids the use of high pollution catalyst, not only reduces three waste discharge, reduces production cost, while product purity is high, and high income has good industrial application value.
Description
Technical field
The present invention relates to the synthetic methods of organo-metallic compound antimony triphenyl.
Background technology
Antimony triphenyl is a kind of important orgnometallic catalyst, is mainly used for catalytic reaction, anti-oxidant, erosion-resisting work
With；It is also the inhibitor of polymerisation, lube oil additive；Its market is wide, economic value is high.
Report in relation to antimony triphenyl synthesis technology is simultaneously few, and the preparation method of antimony triphenyl mainly has at present：
1, Grignard Reagent synthetic method, the method is using chlorobenzene or bromobenzene as raw material, and magnesium powder synthesis of phenyl magnesium halide, then with trichlorine
Change antimony and synthesizes antimony triphenyl.The method reaction condition is harsher, and reaction conversion ratio is low (conversion ratio is less than 80%), and solid waste is difficult to locate
Reason；
2, the toluene solution of German patent DE 508667C propositions sodium is directly reacted with chlorobenzene, antimony trichloride generates triphen
Base antimony.This method is specially：
15 parts by weight sodium melt under 400 parts by weight of toluene, are cooled under stiring about 50 DEG C (300 revs/min).Dropwise plus
Enter the mixed solution of 24.5 parts by weight antimony chlorides, 36.6 parts by weight chlorobenzenes and 20 parts by weight of toluene, reaction temperature is not to be exceeded 50
℃。
After being added dropwise, 70 DEG C~90 DEG C are heated to until sodium is consumed, and is cooled down under continuous stirring.Filtering,
After filtrate concentration, it is settled out the white crystals of triphenyltin.
The method reaction selectivity is only 70%, and by-product is more, and (by-product is mainly biphenyl, polyphenyls, phenyl dichloro
Change antimony, diphenyl antimony chloride), and reaction condition is more difficult to control, metallic sodium is more difficult, and the reaction was complete, and there are certain security risks.
3, document (Journal of Organometallic Chemistry, 1984,270,2,177-183) propose by
Metallic antimony reacts synthesis antimony triphenyl with chlorobenzene under the catalysis of Sodamide.The method expensive raw material price, and reaction yield is not high,
More difficult industrial mass production.
Invention content
The technical problem to be solved in the present invention is to provide a kind of efficient, economic, green, suitable for the three of industrialization production requirements
The synthetic method of phenyl antimony.
In order to solve the above technical problem, the present invention provides a kind of synthetic methods of antimony triphenyl, include following step successively
Suddenly：
(1), under the protection of inert gas, higher fatty acids is added in organic solvent or higher fatty acid salt is (advanced
Aliphatic acid or higher fatty acid salt are a small amount of), and sodium (metallic sodium) is added, first it is heated to reflux (about 70~140
DEG C) 15~60min of stirring (preferably 30~60min), then stop heating, high-speed stirred is until be cooled to room temperature；
(2), under the protection and stirring condition of inert gas, halogeno-benzene is slowly added dropwise into the solution obtained by step (1),
The temperature of control reaction system is no more than 40 DEG C during being added dropwise；After being added dropwise 1~2h is stirred to react in 20~40 DEG C；
(3), under the protection and stirring condition of inert gas, tri-chlorination is slowly added dropwise into the solution obtained by step (2)
The halogenated benzole soln of antimony, time for adding are 30 ± 10 minutes；After being added dropwise 2~4h is stirred to react in 30~130 DEG C；
The sum of the dosage of halogeno-benzene of step (2) and step (3)：Sodium=1:1~2 (preferably 1:1.3~1.5) mole
Than；
The sum of the dosage of halogeno-benzene of step (2) and step (3)：Antimony trichloride=1:0.15~0.5 (preferably 1:0.2
~0.3) molar ratio；
In the halogenated benzole soln of the antimony trichloride, antimony trichloride：Chlorobenzene=0.16：0.25~0.5 mol ratios；
(4), the reaction solution obtained by step (3) is filtered into (remove the slag that desalts), is evaporated off under the filtrate normal pressure of gained organic molten
Agent, halogeno-benzene obtain antimony triphenyl crude product；
The main component of the salt slag is NaCl, NaBr, NaI；
(5), it by the antimony triphenyl crude product petroleum ether dissolution, filters (remove insoluble sludge), the filtrate of gained
Freezing and crystallizing after concentration, obtains antimony triphenyl.
The improvement of synthetic method as antimony triphenyl of the present invention：The halogeno-benzene is chlorobenzene, bromobenzene, iodobenzene.
Synthetic method as antimony triphenyl of the present invention is further improved, in the step (1),
Higher fatty acids is oleic acid, dodecyl benzene sulfonic acid, stearic acid or leukotrienes；
Higher fatty acid salt is enuatrol, dodecyl sodium sulfate or odium stearate；
The advanced fat of 1.5~2.5g of higher fatty acids or adapted of 1.5~2.5ml of organic solvent adapted per 400mL
Fat hydrochlorate；
The sodium of 0.5~1.5mol of organic solvent adapted (preferably 1mol) per 400mL.
Synthetic method as antimony triphenyl of the present invention is further improved：In the step (1), organic solvent is first
Benzene, dimethylbenzene, n-hexane or normal heptane.
Synthetic method as antimony triphenyl of the present invention is further improved, and in the step (5), filtrate is in -20~0 DEG C
Carry out freezing and crystallizing.
Synthetic method as antimony triphenyl of the present invention is further improved, in the step (1), the rotating speed of high-speed stirred
It is 500~1500 revs/min.
Remarks explanation：
There is no the stirring clearly informed in the present invention, is 150~300 revs/min of conventional rotating speed.
In the present invention, nitrogen for example can be selected in inert gas.
The reaction equation of the present invention is as follows：
The present invention has following technical advantage：
(1), using two-step synthesis method, phenyl sodium solution, then the sodium phenide to high concentration are first generated with chlorobenzene and sodium reaction
Antimony trichloride solution, reaction selectivity, conversion ratio higher are added dropwise in solution；
(2), a small amount of higher fatty acids or higher fatty acid salt are added in reacting, makees emulsifier, catalyst, makes reaction more
Add stabilization, reduces the generation of biphenyl and polyphenyls.
(3), purification mode is redissolved using petroleum ether, condensing crystallizing, and product purity is high.
The purity and yield of reaction product antimony triphenyl are high.It is reachable according to the obtained antimony triphenyl yield of this method
98%.
(4), processing step is simply clear, and post-processing is more convenient；
(5), reaction green, metallic sodium can be reacted completely, and waste discharge is few.
In conclusion method using the present invention synthesizes antimony triphenyl, raw material availability is high, avoids high pollution catalyst
Use, not only reduce three waste discharge, reduce production cost, while product purity is high, high income has industry well
Application value.
Specific implementation mode
With reference to specific embodiment, the present invention is described further, but protection scope of the present invention is not limited in
This.
Embodiment 1, a kind of synthetic method of antimony triphenyl, follow the steps below successively：
(1), in anhydrous, anaerobic and have under the protection of nitrogen, 23g (1mol) sodium, 400mL diformazans are added into reaction unit
Benzene and 2.5g sodium stearates are warming up to reflux (137 DEG C) and are stirred with 200 revs/min of speed, stop heating after the 0.5h that flows back,
Then with 500 revs/min of high-speed stirred；Until being cooled to room temperature.
(2), it under the protection and stirring condition of inert gas (nitrogen), is slowly added dropwise into the solution obtained by step (1)
56g (0.5mol) chlorobenzene, the temperature of control reaction system is no more than 40 DEG C during being added dropwise；It is anti-in 30 DEG C of stirrings after being added dropwise
Answer 2h.
(3), 36g (0.16mol) antimony trichloride is taken to be dissolved in 28g (0.25mol) chlorobenzene,
Under the protection and stirring condition of inert gas (nitrogen), trichlorine is slowly added dropwise into the solution obtained by step (2)
Change the chlorobenzene solution of antimony, time for adding is 30 minutes；It is warming up to 120 DEG C after being added dropwise and is stirred to react 2h, that is, stops reaction.
(4), the reaction solution obtained by step (3) is filtered, to remove the slag that desalts, recycling chlorobenzene is evaporated under the filtrate normal pressure of gained
The concentrate of (132 DEG C of evaporating temperatures) and dimethylbenzene (140 DEG C of evaporating temperatures), gained is antimony triphenyl crude product.
(5), by above-mentioned antimony triphenyl crude product, with petroleum ether dissolution, (used in amounts of petroleum ether ensures that being dissolved object is not further added by
Until, about 300ml), it filters again, to remove insoluble sludge, the filtrate of gained is concentrated into after 50ml in -20 DEG C of freezing knots
The crystal of crystalline substance, collection obtains the sterling of antimony triphenyl in 80 DEG C of freeze-day with constant temperature to constant weight.
Yield is 93.7% (in terms of antimony trichloride), purity 99.1%.
Embodiment 2, a kind of synthetic method of antimony triphenyl, follow the steps below successively：
(1), in anhydrous, anaerobic and have under the protection of nitrogen, 23g (1mol) sodium, 400mL first are added into reaction unit
Benzene, 2mL oleic acid are warming up to reflux (110 DEG C) and are stirred with 200 revs/min of speed, stops heating after the 1h that flows back, with 500 revs/min
High-speed stirred；Until being cooled to room temperature.
(2), it under the protection and stirring condition of inert gas (nitrogen), is slowly added dropwise into the solution obtained by step (1)
56g (0.5mol) chlorobenzene, the temperature of control reaction system is no more than 40 DEG C during being added dropwise；In 30 DEG C after being added dropwise, stirring
React 2h.
(3), 36g (0.16mol) antimony trichloride is taken to be dissolved in 28g (0.25mol) chlorobenzene,
Under the protection and stirring condition of inert gas (nitrogen), trichlorine is slowly added dropwise into the solution obtained by step (2)
Change the chlorobenzene solution of antimony, time for adding is 30 minutes；It is warming up to 110 DEG C after being added dropwise and is stirred to react 3h, that is, stops reaction.
(4), the reaction solution obtained by step (3) is filtered, to remove the slag that desalts, recycling chlorobenzene is evaporated under the filtrate normal pressure of gained
And toluene, the concentrate of gained is antimony triphenyl crude product.
The purity of the crude product is only 73.8%.
(5), above-mentioned antimony triphenyl crude product is dissolved with petroleum ether (about 300ml), is filtered again, it is insoluble residual to remove
Slag, the filtrate of gained, to constant weight, obtain in -20 DEG C of freezing and crystallizings, the crystal of collection in 80 DEG C of freeze-day with constant temperature after being concentrated into 50ml
The sterling of antimony triphenyl.
Yield is 98.1%, purity 99.3%.
Embodiment 3, a kind of synthetic method of antimony triphenyl, follow the steps below successively：
(1), in anhydrous, anaerobic and have under the protection of nitrogen, 23g (1mol) sodium, 400mL first are added into reaction unit
Benzene, 2g stearic acid are warming up to reflux (110 DEG C) and are stirred with 200 revs/min of speed, stop heating after the 1h that flows back, with 500 revs/min
High-speed stirred；Until being cooled to room temperature.
(2), it under the protection and stirring condition of inert gas (nitrogen), is slowly added dropwise into the solution obtained by step (1)
78.5g (0.5mol) bromobenzene, the temperature of control reaction system is no more than 40 DEG C during being added dropwise；In 40 DEG C of stirrings after being added dropwise
React 1h.
(3), 36g (0.16mol) antimony trichloride is taken to be dissolved in 78.5g (0.5mol) bromobenzene,
Under the protection and stirring condition of inert gas (nitrogen), trichlorine is slowly added dropwise into the solution obtained by step (2)
Change the bromobenzene solution of antimony, time for adding is 30 minutes；It is warming up to 110 DEG C after being added dropwise and is stirred to react 3h, that is, stops reaction.
(4), the reaction solution obtained by step (3) is filtered, to remove the slag that desalts, recycling bromobenzene is evaporated under the filtrate normal pressure of gained
And toluene, the concentrate of gained is antimony triphenyl crude product.
(5), above-mentioned antimony triphenyl crude product is dissolved with petroleum ether (about 300ml), is filtered again, it is insoluble residual to remove
Slag, the filtrate of gained, to constant weight, obtain in -20 DEG C of freezing and crystallizings, the crystal of collection in 80 DEG C of freeze-day with constant temperature after being concentrated into 50ml
The sterling of antimony triphenyl.
Yield is 96.5%, purity 97.8%.
Embodiment 4, a kind of synthetic method of antimony triphenyl, follow the steps below successively：
(1), in anhydrous, anaerobic and have under the protection of nitrogen, 23g (1mol) sodium, 400mL positive heptan are added into reaction unit
Alkane, 2mL oleic acid are warming up to reflux (99 DEG C) and are stirred with 300 revs/min of speed, stops heating after the 1h that flows back, with 1000 revs/min
High-speed stirred；Until being cooled to room temperature.
(2), it under the protection and stirring condition of inert gas (nitrogen), is slowly added dropwise into the solution obtained by step (1)
56g (0.5mol) chlorobenzene, the temperature of control reaction system is no more than 40 DEG C during being added dropwise；In 30 DEG C after being added dropwise, stirring
React 2h.
(3), 36g (0.16mol) antimony trichloride is taken to be dissolved in 28g (0.25mol) chlorobenzene,
Under the protection and stirring condition of inert gas (nitrogen), trichlorine is slowly added dropwise into the solution obtained by step (2)
Change the chlorobenzene solution of antimony, time for adding is 30 minutes；It is warming up to 99 DEG C after being added dropwise and is stirred to react 3h, that is, stops reaction.
(4), the reaction solution obtained by step (3) is filtered, to remove the slag that desalts, recycling chlorobenzene is evaporated under the filtrate normal pressure of gained
And normal heptane, the concentrate of gained is antimony triphenyl crude product.
(5), above-mentioned antimony triphenyl crude product is dissolved with petroleum ether (about 300ml), is filtered again, it is insoluble residual to remove
Slag, the filtrate of gained, to constant weight, obtain in -20 DEG C of freezing and crystallizings, the crystal of collection in 80 DEG C of freeze-day with constant temperature after being concentrated into 50ml
The sterling of antimony triphenyl.
Yield is 91.1%, purity 98.7%.
Embodiment 5, a kind of synthetic method of antimony triphenyl, follow the steps below successively：
(1), in anhydrous, anaerobic and have under the protection of nitrogen, 23g (1mol) sodium, 400mL diformazans are added into reaction unit
Benzene, 2mL oleic acid are warming up to reflux (137 DEG C) and are stirred with 200 revs/min of speed, stops heating after the 0.5h that flows back, with 500 turns/
The high-speed stirred divided, until being cooled to room temperature.
(2), it under the protection and stirring condition of inert gas (nitrogen), is slowly added dropwise into the solution obtained by step (1)
72.8g (0.65mol) chlorobenzene, the temperature of control reaction system is no more than 40 DEG C during being added dropwise；In 40 DEG C after being added dropwise, stir
Mix reaction 1h.
(3), 36g (0.16mol) antimony trichloride is taken to be dissolved in 28g (0.25mol) chlorobenzene,
Under the protection and stirring condition of inert gas (nitrogen), trichlorine is slowly added dropwise into the solution obtained by step (2)
Change the chlorobenzene solution of antimony, time for adding is 30 minutes；It is warming up to 120 DEG C after being added dropwise and is stirred to react 2h, that is, stops reaction.
(4), the reaction solution obtained by step (3) is filtered, to remove the slag that desalts, recycling chlorobenzene is evaporated under the filtrate normal pressure of gained
And dimethylbenzene, the concentrate of gained is antimony triphenyl crude product.
(5), above-mentioned antimony triphenyl crude product is dissolved with petroleum ether (about 300ml), is filtered again, it is insoluble residual to remove
Slag, the filtrate of gained, to constant weight, obtain in -20 DEG C of freezing and crystallizings, the crystal of collection in 80 DEG C of freeze-day with constant temperature after being concentrated into 50ml
The sterling of antimony triphenyl.
Yield is 93.8%, purity 97.5%.
Embodiment 6, a kind of synthetic method of antimony triphenyl, follow the steps below successively：
(1), in anhydrous, anaerobic and have under the protection of nitrogen, 23g (1mol) sodium, 400mL first are added into reaction unit
Benzene, 2mL oleic acid are warming up to reflux (110 DEG C) and are stirred with 200 revs/min of speed, stops heating after the 1h that flows back, with 500 revs/min
High-speed stirred；Until being cooled to room temperature.
(2), it under the protection and stirring condition of inert gas (nitrogen), is slowly added dropwise into the solution obtained by step (1)
56g (0.5mol) chlorobenzene, the temperature of control reaction system is no more than 40 DEG C during being added dropwise；In 30 DEG C after being added dropwise, stirring
React 2h.
(3), 36g (0.16mol) antimony trichloride is taken to be dissolved in 28g (0.25mol) chlorobenzene,
Under the protection and stirring condition of inert gas (nitrogen), trichlorine is slowly added dropwise into the solution obtained by step (2)
Change the chlorobenzene solution of antimony, time for adding is 30 minutes；It is warming up to 110 DEG C after being added dropwise and is stirred to react 3h, that is, stops reaction.
(4), the reaction solution obtained by step (3) is filtered, to remove the slag that desalts, recycling chlorobenzene is evaporated under the filtrate normal pressure of gained
And dimethylbenzene, the concentrate of gained is antimony triphenyl crude product.
(5), above-mentioned antimony triphenyl crude product is dissolved with petroleum ether (about 300ml), is filtered again, it is insoluble residual to remove
Slag, the filtrate of gained, to constant weight, obtain in -20 DEG C of freezing and crystallizings, the crystal of collection in 80 DEG C of freeze-day with constant temperature after being concentrated into 50ml
The sterling of antimony triphenyl.
Yield is 98.1%, purity 99.3%.
Comparative example 1,
Cancel " reaction for being warming up to reflux " in 2 step of embodiment (1), that is, in anhydrous, anaerobic and have the protection of nitrogen
Under, 23g (1mol) sodium, 400mL toluene, 2mL oleic acid are added into reaction unit, chlorine directly then is slowly added dropwise to reaction unit
Benzene；Remaining is equal to embodiment 2.
Acquired results are：Yield is 79.2%, purity 98.1%.
Comparative example 2,
Cancel the use of " the 2mL oleic acid " in 2 step of embodiment (1)；Remaining is equal to embodiment 2.
Acquired results are：Yield is 89.5%, purity 77.8%.
Comparative example 3,
(2) the step of embodiment 2 and step (3) are changed to following content：
36g (0.16mol) antimony trichlorides are mixed with 84g (0.75mol) chlorobenzene, in inert gas (nitrogen) protection and
Under stirring condition, above-mentioned mixed liquor is slowly added dropwise to the solution obtained by step (1)；The temperature of reaction system is controlled during being added dropwise
No more than 40 DEG C, it is warming up to 110 DEG C after being added dropwise and is stirred to react 4h, that is, stops reaction.Remaining is equal to embodiment 2.
Acquired results are：Yield is 90.5%, purity 87.8%.
Comparative example 4, a kind of synthetic method of antimony triphenyl, follow the steps below successively：
(1), in anhydrous, anaerobic and have under the protection of nitrogen, 23g (1mol) sodium, 400mL first are added into reaction unit
Benzene, 2g stearic acid are warming up to reflux (110 DEG C) and are stirred with 200 revs/min of speed, stop heating after the 1h that flows back, with 500 revs/min
High-speed stirred；Until being cooled to room temperature.
(2), it under the protection and stirring condition of inert gas (nitrogen), is slowly added dropwise into the solution obtained by step (1)
78.5g (0.5mol) bromobenzene, the temperature of control reaction system is no more than 40 DEG C during being added dropwise；In 40 DEG C after being added dropwise, stir
Mix reaction 1h.
(3), 36g (0.16mol) antimony trichloride is taken to be dissolved in 78.5g (0.5mol) bromobenzene,
Under the protection and stirring condition of inert gas (nitrogen), trichlorine is slowly added dropwise into the solution obtained by step (2)
Change the bromobenzene solution of antimony, time for adding is 30 minutes；It is warming up to 110 DEG C after being added dropwise and is stirred to react 3h, that is, stops reaction.
(4), the reaction solution obtained by step (3) is filtered, to remove the slag that desalts, recycling bromobenzene is evaporated under the filtrate normal pressure of gained
And toluene, concentrate crystallisation by cooling, filtering by filter cake in 80 DEG C of freeze-day with constant temperature to constant weight, obtain antimony triphenyl product.
Yield is 95.4%, purity 83.1%.
Finally, it should also be noted that it is listed above be only the present invention several specific embodiments.Obviously, this hair
Bright to be not limited to above example, acceptable there are many deformations.Those skilled in the art can be from present disclosure
All deformations for directly exporting or associating, are considered as protection scope of the present invention.
Claims (6)
1. the synthetic method of antimony triphenyl, it is characterized in that including the following steps successively：
(1), under the protection of inert gas, higher fatty acids or higher fatty acid salt are added in organic solvent, and be added
Sodium is first heated to 15~60min of return stirring, then stops heating, and high-speed stirred is until be cooled to room temperature；
(2), under the protection and stirring condition of inert gas, halogeno-benzene is slowly added dropwise into the solution obtained by step (1), is added dropwise
The temperature of control reaction system is no more than 40 DEG C in the process；After being added dropwise 1~2h is stirred to react in 20~40 DEG C；
(3), under the protection and stirring condition of inert gas, antimony trichloride is slowly added dropwise into the solution obtained by step (2)
Halogenated benzole soln, time for adding are 30 ± 10 minutes；After being added dropwise 2~4h is stirred to react in 30~130 DEG C；
The sum of the dosage of halogeno-benzene of step (2) and step (3)：Sodium=1:1~2 molar ratio；
The sum of the dosage of halogeno-benzene of step (2) and step (3)：Antimony trichloride=1:0.15~0.5 molar ratio；
(4), the reaction solution obtained by step (3) is filtered, organic solvent, halogeno-benzene is evaporated off under the filtrate normal pressure of gained, obtains three
Phenyl antimony crude product；
(5), it by the antimony triphenyl crude product petroleum ether dissolution, filters, freezing and crystallizing after the filtrate concentration of gained obtains triphen
Base antimony.
2. the synthetic method of antimony triphenyl according to claim 1, it is characterized in that：
The halogeno-benzene is chlorobenzene, bromobenzene, iodobenzene.
3. the synthetic method of antimony triphenyl according to claim 2, it is characterized in that：
In the step (1),
Higher fatty acids is oleic acid, dodecyl benzene sulfonic acid, stearic acid or leukotrienes；
Higher fatty acid salt is enuatrol, dodecyl sodium sulfate or odium stearate；
The higher fatty acids of 1.5~2.5g of higher fatty acids or adapted of 1.5~2.5ml of organic solvent adapted per 400mL
Salt；
The sodium of 0.5~1.5mol of organic solvent adapted per 400mL.
4. the synthetic method of antimony triphenyl according to claim 3, it is characterized in that：
In the step (1), organic solvent is toluene, dimethylbenzene, n-hexane or normal heptane.
5. the synthetic method of antimony triphenyl according to any one of claims 1 to 4, it is characterized in that：
In the step (5), filtrate carries out freezing and crystallizing in -20~0 DEG C.
6. the synthetic method of antimony triphenyl according to claim 5, it is characterized in that：
In the step (1), the rotating speed of high-speed stirred is 500~1500 revs/min.
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| DE508667C (en) * | 1926-10-28 | 1930-09-29 | I G Farbenindustrie Akt Ges | Process for the preparation of organometallic compounds |
| US3057894A (en) * | 1959-01-05 | 1962-10-09 | Ethyl Corp | Production of organometallic compounds |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| DE508667C (en) * | 1926-10-28 | 1930-09-29 | I G Farbenindustrie Akt Ges | Process for the preparation of organometallic compounds |
| US3057894A (en) * | 1959-01-05 | 1962-10-09 | Ethyl Corp | Production of organometallic compounds |
| CS159322B1 (en) * | 1973-07-02 | 1975-01-31 | ||
| SU642317A1 (en) * | 1976-12-13 | 1979-01-15 | Предприятие П/Я А-7815 | Method of obtaining triphenylstibium |
| CN101643378A (en) * | 2009-09-02 | 2010-02-10 | 中国农业大学 | Method for synthesizing aryl-linking compound |
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