CN109608484A - The quenching method of active metal sodium or lithium - Google Patents
The quenching method of active metal sodium or lithium Download PDFInfo
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- CN109608484A CN109608484A CN201811576605.XA CN201811576605A CN109608484A CN 109608484 A CN109608484 A CN 109608484A CN 201811576605 A CN201811576605 A CN 201811576605A CN 109608484 A CN109608484 A CN 109608484A
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- quenched
- lithium
- quenching method
- reaction
- metallic sodium
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- 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 title claims abstract description 41
- 229910052708 sodium Inorganic materials 0.000 title claims abstract description 41
- 239000011734 sodium Substances 0.000 title claims abstract description 41
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 31
- 238000000034 method Methods 0.000 title claims abstract description 24
- 238000010791 quenching Methods 0.000 title claims abstract description 22
- 230000000171 quenching effect Effects 0.000 title claims abstract description 22
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 21
- 239000002184 metal Substances 0.000 title claims abstract description 21
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims abstract description 47
- 150000008282 halocarbons Chemical class 0.000 claims abstract description 14
- 150000001335 aliphatic alkanes Chemical class 0.000 claims abstract description 5
- 238000001914 filtration Methods 0.000 claims description 16
- 239000007787 solid Substances 0.000 claims description 13
- -1 C1-8 alkyl alkyl chloride Chemical class 0.000 claims description 6
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical class ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 claims description 4
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-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
- 150000001348 alkyl chlorides Chemical class 0.000 claims description 2
- GZUXJHMPEANEGY-UHFFFAOYSA-N bromomethane Chemical compound BrC GZUXJHMPEANEGY-UHFFFAOYSA-N 0.000 claims description 2
- 239000000463 material Substances 0.000 claims description 2
- 238000005859 coupling reaction Methods 0.000 abstract description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 5
- 230000003321 amplification Effects 0.000 abstract description 4
- 238000003199 nucleic acid amplification method Methods 0.000 abstract description 4
- 239000001257 hydrogen Substances 0.000 abstract description 3
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 150000003254 radicals Chemical class 0.000 abstract description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052736 halogen Inorganic materials 0.000 abstract description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 60
- 239000000243 solution Substances 0.000 description 23
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- 239000007788 liquid Substances 0.000 description 10
- 238000010792 warming Methods 0.000 description 10
- 238000003756 stirring Methods 0.000 description 9
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- 238000004821 distillation Methods 0.000 description 7
- 238000002372 labelling Methods 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 230000004044 response Effects 0.000 description 7
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 6
- 230000008878 coupling Effects 0.000 description 6
- 238000010168 coupling process Methods 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 5
- 239000000706 filtrate Substances 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 238000010992 reflux Methods 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 description 4
- 235000019441 ethanol Nutrition 0.000 description 4
- VYAJQQLLLCSMJL-UHFFFAOYSA-N n-[chloro(dimethylamino)boranyl]-n-methylmethanamine Chemical class CN(C)B(Cl)N(C)C VYAJQQLLLCSMJL-UHFFFAOYSA-N 0.000 description 4
- IVDFJHOHABJVEH-UHFFFAOYSA-N pinacol Chemical compound CC(C)(O)C(C)(C)O IVDFJHOHABJVEH-UHFFFAOYSA-N 0.000 description 4
- SIXNTGDWLSRMIC-UHFFFAOYSA-N sodium;toluene Chemical compound [Na].CC1=CC=CC=C1 SIXNTGDWLSRMIC-UHFFFAOYSA-N 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 229910052796 boron Inorganic materials 0.000 description 3
- 239000012295 chemical reaction liquid Substances 0.000 description 3
- 230000009849 deactivation Effects 0.000 description 3
- 230000006837 decompression Effects 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- YCIMNLLNPGFGHC-UHFFFAOYSA-N o-dihydroxy-benzene Natural products OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 3
- 235000002639 sodium chloride Nutrition 0.000 description 3
- 238000005292 vacuum distillation Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- JIGUICYYOYEXFS-UHFFFAOYSA-N 3-tert-butylbenzene-1,2-diol Chemical compound CC(C)(C)C1=CC=CC(O)=C1O JIGUICYYOYEXFS-UHFFFAOYSA-N 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- JEYWNNAZDLFBFF-UHFFFAOYSA-N Nafoxidine Chemical compound C1CC2=CC(OC)=CC=C2C(C=2C=CC(OCCN3CCCC3)=CC=2)=C1C1=CC=CC=C1 JEYWNNAZDLFBFF-UHFFFAOYSA-N 0.000 description 2
- 230000005784 autoimmunity Effects 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical class OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 2
- ILAHWRKJUDSMFH-UHFFFAOYSA-N boron tribromide Chemical class BrB(Br)Br ILAHWRKJUDSMFH-UHFFFAOYSA-N 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 229960000935 dehydrated alcohol Drugs 0.000 description 2
- 229960004756 ethanol Drugs 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- UNFUYWDGSFDHCW-UHFFFAOYSA-N monochlorocyclohexane Chemical compound ClC1CCCCC1 UNFUYWDGSFDHCW-UHFFFAOYSA-N 0.000 description 2
- UBDPZBLACZIAPS-UHFFFAOYSA-N n-[bromo(dimethylamino)boranyl]-n-methylmethanamine Chemical class CN(C)B(Br)N(C)C UBDPZBLACZIAPS-UHFFFAOYSA-N 0.000 description 2
- 229950002366 nafoxidine Drugs 0.000 description 2
- 238000005580 one pot reaction Methods 0.000 description 2
- HXITXNWTGFUOAU-UHFFFAOYSA-N phenylboronic acid Chemical compound OB(O)C1=CC=CC=C1 HXITXNWTGFUOAU-UHFFFAOYSA-N 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 208000011580 syndromic disease Diseases 0.000 description 2
- 238000010257 thawing Methods 0.000 description 2
- 230000001960 triggered effect Effects 0.000 description 2
- MNDIARAMWBIKFW-UHFFFAOYSA-N 1-bromohexane Chemical compound CCCCCCBr MNDIARAMWBIKFW-UHFFFAOYSA-N 0.000 description 1
- ZZPNDIHOQDQVNU-UHFFFAOYSA-N 2-hydroxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane Chemical compound CC1(C)OB(O)OC1(C)C ZZPNDIHOQDQVNU-UHFFFAOYSA-N 0.000 description 1
- PVFOHMXILQEIHX-UHFFFAOYSA-N 8-[(6-bromo-1,3-benzodioxol-5-yl)sulfanyl]-9-[2-(2-bromophenyl)ethyl]purin-6-amine Chemical compound C=1C=2OCOC=2C=C(Br)C=1SC1=NC=2C(N)=NC=NC=2N1CCC1=CC=CC=C1Br PVFOHMXILQEIHX-UHFFFAOYSA-N 0.000 description 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- 238000006069 Suzuki reaction reaction Methods 0.000 description 1
- 238000010521 absorption reaction Methods 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
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000011260 aqueous acid Substances 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 230000031709 bromination Effects 0.000 description 1
- 238000005893 bromination reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- NDTCXABJQNJPCF-UHFFFAOYSA-N chlorocyclopentane Chemical compound ClC1CCCC1 NDTCXABJQNJPCF-UHFFFAOYSA-N 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 125000004494 ethyl ester group Chemical group 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 230000026030 halogenation Effects 0.000 description 1
- 238000005658 halogenation reaction Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- QTBFPMKWQKYFLR-UHFFFAOYSA-N isobutyl chloride Chemical compound CC(C)CCl QTBFPMKWQKYFLR-UHFFFAOYSA-N 0.000 description 1
- 238000005304 joining Methods 0.000 description 1
- VVNXEADCOVSAER-UHFFFAOYSA-N lithium sodium Chemical compound [Li].[Na] VVNXEADCOVSAER-UHFFFAOYSA-N 0.000 description 1
- 238000005360 mashing Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 229940050176 methyl chloride Drugs 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- VRJQRYVDHIMICK-UHFFFAOYSA-N n-dichloroboranyl-n-methylmethanamine Chemical compound CN(C)B(Cl)Cl VRJQRYVDHIMICK-UHFFFAOYSA-N 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000011833 salt mixture Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- FAQYAMRNWDIXMY-UHFFFAOYSA-N trichloroborane Chemical class ClB(Cl)Cl FAQYAMRNWDIXMY-UHFFFAOYSA-N 0.000 description 1
- 239000002699 waste material 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
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/02—Boron compounds
- C07F5/022—Boron compounds without C-boron linkages
-
- 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
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/02—Boron compounds
- C07F5/027—Organoboranes and organoborohydrides
-
- 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
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/02—Boron compounds
- C07F5/04—Esters of boric acids
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
Abstract
The invention discloses active metal sodium or lithium quenching methods.In the halogen lithium exchange reactions that the free radical coupling reaction or lithium metal that are participated in using metallic sodium are participated in, reaction terminates usually to carry out safe be quenched to excess activity metal, excessive metallic sodium and lithium are quenched using halogenated hydrocarbons, avoid conventionally employed water or when alcohol is quenched hydrogen generation, operating safety factor increases.This method is easy to operate, and the coupled alkane of generation does not influence reaction treatment, and use is quenched in suitable industrial amplification production.
Description
Technical field
The present invention relates to the quenching methods of active metal to belong to more particularly, to active metal sodium or the quenching method of lithium
Treatment process field is quenched in Organometallic Chemistry.
Background technique
Join borate: including connection boric acid pinacol ester, joining boric acid neopentyl glycol ester and connection boric acid catechol ester etc., as
The important coupling additive of Suzuki coupling has been sent out since coupling reaction acquisition Nobel chemistry Prize in 2010 using increasing
Exhibition is swift and violent.In recent years, with the continuous propulsion of Green Chemistry, two boron of tetrahydroxy is as simplest molecule list in connection boric acid series
Member is more widely applied.
However, in existing synthetic method the coupling step using metallic sodium will be undergone without exception, for example, by using double
(dimethylamino) boron chloride or bis- (dimethylamino) boron bromides use metallic sodium to carry out itself under counterflow condition in toluene solvant
Coupling；Or autoimmunity syndrome occurs for back flow reaction in toluene solvant in metallic sodium using bis- (nafoxidine) boron bromides；Or
Autoimmunity syndrome is carried out using toluene solvant in metallic sodium using 3- tert-butyl catechol boron chloride.After above-mentioned three's coupling
The intermediate arrived is then reacted from different glycol, catechol or acid, obtains above-mentioned boric acid series of products.
Metallic sodium is all made of slightly excessive state in above-mentioned reaction, after reaction in excessive metallic sodium and reaction process
The sodium chloride and sodium bromide of generation mix, and such as will bring very big security risk without being quenched in time, also there is document
Middle reaction terminates directly filtering (there is also obvious security risks for filtering itself, and not filtering directly distillation danger will be more significant)
Afterwards, it is carefully quenched, is referred to using dehydrated alcohol: Organic Syntheses, Coll. Vol. 10, p.115
(2004); Vol. 77, p.176 (2000).For industry amplification, being quenched is the operation for having to carry out, however is adopted
It is directly quenched with water and ethyl alcohol etc., first is that low efficiency, generates a large amount of salkali waste and salt mixture, cannot achieve effective benefit of resource
With；Second is that security risk is obvious, the hydrogen directly generated is quenched and easily causes the potential security risks such as explosion.
It is after reaction, excessive using lithium metal and halogenation boron one pot reaction during synthesizing organic boronic
The mode also generallyd use similar to metallic sodium is quenched in lithium metal, after reaction solution filtering, water is added or ethyl alcohol is quenched, or
The addition aqueous acid directly in reaction solution is not filtered to be quenched.Above-mentioned to be quenched in mode, the former exists same as metallic sodium
The problem of, there is also the risk for being reduced directly groups certain in product (such as nitro, alkene etc.) when the latter is quenched, increase
Product isolates and purifies difficulty.
It is then desired to develop means safely and effectively are quenched just seeming very for above-mentioned excess activity species metallic sodium or lithium
It is necessary.
Summary of the invention
In order to overcome drawbacks described above, the present invention provides carried out using halogenated hydrocarbons to excessive active metal species sodium or lithium
The method being quenched, this method is easy to operate, and the coupled alkane of generation does not influence reaction treatment, and suitable industrial amplification production is quenched
Using.
The quenching method of active metal sodium or lithium, which is characterized in that using halogenated hydrocarbons to containing active metal sodium or lithium
System is quenched.
In the above-mentioned technical solutions, the reaction system being quenched, including the consolidating containing active metal species obtained after filtering
Body or solution, and the reaction solution with active metal species etc..
Further, halogenated hydrocarbons includes the alkyl chloride containing C1-C15, bromo-derivative or idoalkane.Preferably C1-C8 alkyl
Alkyl chloride or bromoalkane.
Further, in the above-mentioned technical solutions, it is quenched and needs to control certain temperature, metallic sodium or lithium metal, which are quenched, to be adopted
It is carried out at -20 DEG C to 150 DEG C, is carried out using being added dropwise or being slowly added to mode.After material to be added causes, it is further continued for steadily dripping
Add, until being quenched completely.
Further preferably, metallic sodium uses carries out at 30-150 DEG C；It is carried out at -10 DEG C to 40 DEG C of lithium metal use.
Further, in the above-mentioned technical solutions, halogenated hydrocarbons additional amount is 1-2 times of active metal theoretical residual.It is excellent
1-1.2 times is selected to measure.
Preferably, in the above-mentioned technical solutions, it after metallic sodium coupling reaction liquid being directly quenched, is filtered, then carries out
The mode of distillation carries out safer reliable.To the reaction solution after lithium metal one pot reaction by bottom blowing, by lithium metal
After bits retain, solvent is added and halogenated hydrocarbons is quenched.It is chloromethanes or bromine first that halogenated hydrocarbons, which is preferably quenched, in the mode being directly quenched
Alkane.
The principle of above-mentioned quenching reaction is after free radical coupling occurs using metallic sodium and metal halide object, by excess activity
Metal steadily consumes, and reaches safety and purpose is quenched.It is then to make full use of lithium metal anti-with halogenated hydrocarbons for being quenched for lithium metal
After answering there is half-life period in lithium alkylide in common solvents, by itself degenerating after heating, can also be suitably added alcohols
Accelerate reaction, that is, can reach and destruction is quenched.
The good effect that the present invention generates
The invention discloses active metal sodium or lithium quenching methods.In the free radical coupling reaction or metal participated in using metallic sodium
Lithium participate in halogen lithium exchange reactions when, reaction terminate usually to excess activity metal carry out safety is quenched, excessive metallic sodium and
Lithium is quenched using halogenated hydrocarbons, avoid conventionally employed water or when alcohol is quenched hydrogen generation, operating safety factor increases.It should
Method is easy to operate, and the coupled alkane of generation does not influence reaction treatment, and use is quenched in suitable industrial amplification production.
Specific embodiment
1 reaction equation of embodiment is as follows:
Under nitrogen protection, by metallic sodium (2.6g, 0.11mol) and 20mL toluene, it is heated to 100 DEG C and is dissolved completely to metallic sodium
Afterwards, starting quickly stirring, it is further heated up to 105-110 DEG C.Bis- (nafoxidine) boron bromide (21.8g, 0.094mol) dissolutions
In 6mL toluene, start to be added dropwise in above-mentioned metallic sodium toluene solution, keep weak reflux state during being added dropwise, be added dropwise,
Insulated and stirred 3-5 hours, system was navy blue, and sample GC is taken to detect end of reaction, labeling response liquid internal standard yield 79%.At this time
It is added dropwise to chlorocyclopentane (0.4mol)/toluene (15mL) solution, is added dropwise, is stirred to react 2 hours, at this time labeling response liquid
Internal standard yield 78%, filtering, solid are washed using toluene, and after distilling low boiling impurity, normal heptane is added in filtrate decompression distillation
55mL is gradually cooled to -20 DEG C hereinafter, light yellow solid coupled product 10.1g, yield 71% is obtained by filtration under stirring.
The solid obtained after filtering is added go out no heat release and gas of water quenching and generates, it was demonstrated that complete deactivation.
2 reaction equation of embodiment is as follows:
Under nitrogen protection, metallic sodium (22.3g, 0.97mol) and 78mL toluene are added in reaction flask, is warming up to metallic sodium thawing
Afterwards, start to be warming up to 105-110 DEG C under quickly stirring, bis- (dimethylamino) boron bromides (135.6g, 0.76mol) are dissolved in
In 55mL toluene, start to be added dropwise in above-mentioned metallic sodium toluene solution, keep weak reflux state during being added dropwise, be added dropwise,
Insulated and stirred 3-5 hours, system was navy blue, and sample GC is taken to detect end of reaction, labeling response liquid internal standard yield 80%.At this time
It is added dropwise to bromo n-hexane (0.6mol)/toluene (70mL) solution, after to be triggered, rate of addition can be accelerated, dripped within about 1 hour
Finish, is stirred to react 2 hours, labeling response liquid internal standard yield 78%, filtering, solid are washed using toluene 150mL at this time, and filtrate subtracts
Pressure distillation, after low boiling impurity is distilled, then oil bath is warming up to 120-140 DEG C, and vacuum distillation obtains colourless liquid coupling and produces
Object 55g, yield 72%.
The solid obtained after filtering is added go out no heat release and gas of water quenching and generates, it was demonstrated that complete deactivation.Pass through drop
Setting analysis, bromination sodium content is in 98-101% in solid.
3 reaction equation of embodiment is as follows:
Under nitrogen protection, metallic sodium (36g, 1.6mol) and 144mL dimethylbenzene are added in reaction flask, is warming up to metallic sodium and melts
After change, start to be warming up to 135-145 DEG C under quickly stirring, bis- (dimethylamino) boron chlorides (190g, 1.4mol) are dissolved in 95mL
In dimethylbenzene, start to be added dropwise in above-mentioned metallic sodium toluene solution, keep weak reflux state during being added dropwise, be added dropwise, protects
Temperature stirring 3-5 hours, system is navy blue, and sample GC is taken to detect end of reaction, labeling response liquid internal standard yield 83%.It drips at this time
Isobutyl chloride (0.4mol)/toluene (110mL) solution is added, without obvious elicitation procedure when dropwise addition, is added dropwise, is stirred to react 2-
3 hours, labeling response liquid internal standard yield 83%, filtering, solid were washed using toluene 180mL at this time, and filtrate decompression distillation will be low
After boiling contaminants distillation, then oil bath is warming up to 120-140 DEG C, and vacuum distillation obtains colourless liquid coupled product 105g, yield
75%。
The solid obtained after filtering is added go out no heat release and gas of water quenching and generates, it was demonstrated that complete deactivation.
4 reaction equation of embodiment is as follows:
Under nitrogen protection, metallic sodium (29.8g, 1.3mol) and 144mL toluene are added in reaction flask, is warming up to metallic sodium thawing
Afterwards, start to be warming up to 105-110 DEG C under quickly stirring, bis- (3- tert-butyl catechol) boron chlorides (181.0g, 0.86mol)
It is dissolved in 160mL toluene, starts to be added dropwise in above-mentioned metallic sodium toluene solution, keep weak reflux state during being added dropwise, drip
Add complete, insulated and stirred 5-8 hours, system was navy blue, and sample GC is taken to detect end of reaction, labeling response liquid internal standard yield
94%.It is filtered under enclosed system, solid is washed using toluene 150mL, and filtrate decompression distillation after distilling low boiling impurity, is added
After heptane filters again, vacuum distillation solvent obtains solid coupled product 152g, yield 87%.
The metallic sodium and sodium chloride hybrid solid obtained after reaction system filtering after toluene is added, is warming up to 60 DEG C, is added dropwise
Enter chlorocyclohexane (1.0mol)/toluene (220mL) solution, after to be triggered, rate of addition can be accelerated, dripped within about 1.5 hours
Finish, be stirred to react 3-5 hour, be cooled to room temperature, go out no heat release and gas of water quenching is added at this time and generates, it was demonstrated that mistake completely
It is living.
5 reaction equation of embodiment is as follows:
Under nitrogen protection, lithium metal (15.2g, 0.22mol) and tetrahydrofuran 220mL, stirring decline are added in reaction flask
Temperature to -10 DEG C starts that bromobenzene (16.5g, 0.105mol) and the dissolution of bis- (dimethylamino) boron chlorides (14.8g, 0.11mol) is added dropwise
Mixed solution in 140mL tetrahydrofuran, is added dropwise, and insulated and stirred is reacted 3-5 hours, after detecting fully reacting, reaction
Liquid internal standard yield is 83%.Reducing reaction temperature again is 0 DEG C, is passed through methyl chloride gas until system there is no until absorption, so
It is warmed to room temperature and is stirred overnight naturally afterwards, detecting reaction solution internal standard yield at this time is 83%, is cooled to 0 DEG C, and 8% aqueous hydrochloric acid solution is added dropwise
PH=3-4, ethyl acetate 60mL extraction are adjusted, saturated common salt washing rotates heptane and toluene (volume ratio 10:1) mashing after solvent,
Obtain off-white powder phenyl boric acid 9.5g, yield 74%.
6 reaction equation of embodiment is as follows:
Under nitrogen protection, lithium metal (16.6g, 0.24mol) and tetrahydrofuran 220mL, stirring decline are added in reaction flask
Temperature to -10 DEG C starts that bromobenzene (16.5g, 0.105mol) and the dissolution of bis- (dimethylamino) boron chlorides (14.8g, 0.11mol) is added dropwise
Mixed solution in 140mL tetrahydrofuran, is added dropwise, and insulated and stirred is reacted 3-5 hours, after detecting fully reacting, reaction
Liquid internal standard yield is 83%.Reducing reaction temperature again is 0 DEG C, is added dropwise to bromomethane (0.04mol), is then warmed to room temperature naturally
It is stirred overnight, detecting reaction solution internal standard yield at this time is 81%, is cooled to 0 DEG C, and 10% aqueous hydrochloric acid solution tune pH=3-4, acetic acid is added dropwise
Ethyl ester 60mL extraction, twice, saturated common salt washing obtains off-white powder phenyl boric acid 9.7g, yield after rotating solvent for washing
76%。
7 reaction equation of embodiment is as follows:
Under nitrogen protection, metallic sodium (5.7g, 0.25mol) and toluene 140mL are added in reaction flask, is warming up under stirring
100-105 DEG C, start to be added dropwise 1- chlorine cyclohexene (11.6g, 0.1mol) and bis- (dimethylamino) boron chlorides (20.1g,
0.15mol) mixed solution keeps weak reflux state during being added dropwise, it is to note that dropwise addition is too fast to cause slug.It is added dropwise, protects
Temperature is stirred to react 2 hours, and after detecting fully reacting, after reaction solution pinacol is derivative, internal standard yield is 77%.Then it is dripped in 1 hour
Add chlorocyclohexane (0.2mol), temperature no longer changes when the later period is added dropwise, and sealing filtering, solid salt instills dehydrated alcohol after filtering
Afterwards, active component is not detected.Pinacol (17.6g, 0.15mol) is added temperature reaction 2 hours in filtrate, and GC detection has been reacted
Finish, reaction solution internal standard yield is 74% at this time, after rotating solvent, sulfolane is added and is evaporated under reduced pressure to obtain colourless oil liquid hexamethylene
Alkene -1- boric acid pinacol ester 14.6g, yield 70%.
Embodiment above describes basic principles and main features of the invention and advantages.The technical staff of the industry should
Understand, the present invention is not limited to the above embodiments, and the above embodiments and description only describe originals of the invention
Reason, under the range for not departing from the principle of the invention, various changes and improvements may be made to the invention, these changes and improvements are each fallen within
In the scope of protection of the invention.
Claims (10)
1. the quenching method of active metal sodium or lithium, it is characterised in that: using halogenated hydrocarbons to the body containing active metal sodium or lithium
System is quenched.
2. quenching method according to claim 1, it is characterised in that: the reaction system being quenched, including what is obtained after filtering
Solid or solution containing active metal species, and the reaction solution with active metal.
3. quenching method according to claim 1, it is characterised in that: halogenated hydrocarbons includes the alkyl chloride containing C1-C15, bromine
For object or idoalkane.
4. quenching method according to claim 3, it is characterised in that: halogenated hydrocarbons be include C1-8 alkyl alkyl chloride or bromine
For alkane.
5. quenching method according to claim 4, it is characterised in that: metallic sodium be quenched selected from C1-C8 alkyl alkyl chloride or
Bromoalkane, lithium metal are quenched selected from chloromethanes or bromomethane.
6. quenching method according to claim 1, it is characterised in that: need to control certain temperature, object to be added when being quenched
It after material causes, is further continued for steadily being added dropwise, until being quenched completely.
7. quenching method according to claim 5, it is characterised in that: temperature is quenched and is carried out at -20 DEG C to 150 DEG C,
Mode is quenched using dropwise addition or is slowly added to.
8. quenching method according to claim 1, it is characterised in that: metallic sodium uses to carry out at 30 DEG C to 150 DEG C；Metal
It is carried out at -20 DEG C to 40 DEG C of lithium use.
9. quenching method according to claim 1, it is characterised in that: halogenated hydrocarbons additional amount is that metallic sodium or lithium are theoretical remaining
1-5 times of amount.
10. quenching method according to claim 9, it is characterised in that: halogenated hydrocarbons additional amount is that metallic sodium or lithium theory are surplus
1-1.2 times of surplus.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112250702A (en) * | 2020-11-28 | 2021-01-22 | 沧州普瑞东方科技有限公司 | Preparation method of 1, 3-propylene glycol o-cyanobenzene borate |
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| CN101077874A (en) * | 2006-05-26 | 2007-11-28 | 中国石油化工集团公司 | Preparation method for lithium alkyl |
| JP2010111550A (en) * | 2008-11-07 | 2010-05-20 | Ube Ind Ltd | High-purity boron trichloride and production method thereof |
| CN107118225A (en) * | 2017-05-17 | 2017-09-01 | 成都化润药业有限公司 | A kind of security processing for the metallic sodium for preventing hydrogen generation |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101077874A (en) * | 2006-05-26 | 2007-11-28 | 中国石油化工集团公司 | Preparation method for lithium alkyl |
| JP2010111550A (en) * | 2008-11-07 | 2010-05-20 | Ube Ind Ltd | High-purity boron trichloride and production method thereof |
| CN107118225A (en) * | 2017-05-17 | 2017-09-01 | 成都化润药业有限公司 | A kind of security processing for the metallic sodium for preventing hydrogen generation |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112250702A (en) * | 2020-11-28 | 2021-01-22 | 沧州普瑞东方科技有限公司 | Preparation method of 1, 3-propylene glycol o-cyanobenzene borate |
| CN112250702B (en) * | 2020-11-28 | 2023-07-25 | 沧州普瑞东方科技有限公司 | Preparation method of o-nitrilo-phenylboronic acid-1, 3-propanediol ester |
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