CN114874099A - Preparation method of alkane chloride - Google Patents
Preparation method of alkane chloride Download PDFInfo
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- CN114874099A CN114874099A CN202210162171.9A CN202210162171A CN114874099A CN 114874099 A CN114874099 A CN 114874099A CN 202210162171 A CN202210162171 A CN 202210162171A CN 114874099 A CN114874099 A CN 114874099A
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- -1 alkane chloride Chemical class 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims abstract description 65
- 239000000460 chlorine Substances 0.000 claims abstract description 45
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 41
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000002904 solvent Substances 0.000 claims abstract description 25
- 150000001335 aliphatic alkanes Chemical class 0.000 claims abstract description 21
- 239000002253 acid Substances 0.000 claims abstract description 14
- 239000003054 catalyst Substances 0.000 claims abstract description 14
- 150000001875 compounds Chemical class 0.000 claims abstract description 14
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000001301 oxygen Substances 0.000 claims abstract description 8
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 8
- 238000005286 illumination Methods 0.000 claims abstract description 6
- 238000001035 drying Methods 0.000 claims abstract description 4
- 238000001914 filtration Methods 0.000 claims abstract description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 17
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 claims description 12
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 8
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 claims description 8
- 229910002651 NO3 Inorganic materials 0.000 claims description 7
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 230000002378 acidificating effect Effects 0.000 claims description 4
- 230000007935 neutral effect Effects 0.000 claims description 4
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 4
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 4
- 239000011347 resin Substances 0.000 claims description 4
- 229920005989 resin Polymers 0.000 claims description 4
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims description 3
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- IOVCWXUNBOPUCH-UHFFFAOYSA-N Nitrous acid Chemical compound ON=O IOVCWXUNBOPUCH-UHFFFAOYSA-N 0.000 claims description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 2
- 239000000463 material Substances 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 150000007524 organic acids Chemical class 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 239000000741 silica gel Substances 0.000 claims description 2
- 229910002027 silica gel Inorganic materials 0.000 claims description 2
- 238000004821 distillation Methods 0.000 claims 1
- 238000000605 extraction Methods 0.000 claims 1
- 238000000926 separation method Methods 0.000 claims 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 abstract description 40
- 238000003756 stirring Methods 0.000 abstract description 24
- 239000011780 sodium chloride Substances 0.000 abstract description 20
- 239000007800 oxidant agent Substances 0.000 abstract description 16
- 230000001590 oxidative effect Effects 0.000 abstract description 11
- 230000007613 environmental effect Effects 0.000 abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 3
- 150000002148 esters Chemical class 0.000 abstract description 2
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 36
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 32
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 19
- 230000001376 precipitating effect Effects 0.000 description 18
- 235000010288 sodium nitrite Nutrition 0.000 description 18
- 239000006228 supernatant Substances 0.000 description 18
- 238000005481 NMR spectroscopy Methods 0.000 description 17
- 229940098779 methanesulfonic acid Drugs 0.000 description 16
- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 description 14
- 239000007858 starting material Substances 0.000 description 11
- JSZOAYXJRCEYSX-UHFFFAOYSA-N 1-nitropropane Chemical compound CCC[N+]([O-])=O JSZOAYXJRCEYSX-UHFFFAOYSA-N 0.000 description 9
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 8
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 8
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- 239000003153 chemical reaction reagent Substances 0.000 description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 238000005660 chlorination reaction Methods 0.000 description 4
- 125000001309 chloro group Chemical group Cl* 0.000 description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 4
- 238000007789 sealing Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- AIMREYQYBFBEGQ-UHFFFAOYSA-N 2-methyl-2-nitropropane Chemical compound CC(C)(C)[N+]([O-])=O AIMREYQYBFBEGQ-UHFFFAOYSA-N 0.000 description 2
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 2
- RJUFJBKOKNCXHH-UHFFFAOYSA-N Methyl propionate Chemical compound CCC(=O)OC RJUFJBKOKNCXHH-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- CPFYYCSSFPWSNB-UHFFFAOYSA-N amino 2-aminopropanoate Chemical compound CC(N)C(=O)ON CPFYYCSSFPWSNB-UHFFFAOYSA-N 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 229940017219 methyl propionate Drugs 0.000 description 2
- 239000002808 molecular sieve Substances 0.000 description 2
- MCSAJNNLRCFZED-UHFFFAOYSA-N nitroethane Chemical compound CC[N+]([O-])=O MCSAJNNLRCFZED-UHFFFAOYSA-N 0.000 description 2
- 239000011368 organic material Substances 0.000 description 2
- IUGYQRQAERSCNH-UHFFFAOYSA-N pivalic acid Chemical compound CC(C)(C)C(O)=O IUGYQRQAERSCNH-UHFFFAOYSA-N 0.000 description 2
- JAMNHZBIQDNHMM-UHFFFAOYSA-N pivalonitrile Chemical compound CC(C)(C)C#N JAMNHZBIQDNHMM-UHFFFAOYSA-N 0.000 description 2
- 235000019260 propionic acid Nutrition 0.000 description 2
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- NBRKLOOSMBRFMH-UHFFFAOYSA-N tert-butyl chloride Chemical compound CC(C)(C)Cl NBRKLOOSMBRFMH-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- QCYOIFVBYZNUNW-BYPYZUCNSA-N N,N-dimethyl-L-alanine Chemical compound CN(C)[C@@H](C)C(O)=O QCYOIFVBYZNUNW-BYPYZUCNSA-N 0.000 description 1
- 239000005708 Sodium hypochlorite Substances 0.000 description 1
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- KNWIDSLTUVLFSP-UHFFFAOYSA-N azanium;2,2-dimethylpropanoate Chemical compound [NH4+].CC(C)(C)C([O-])=O KNWIDSLTUVLFSP-UHFFFAOYSA-N 0.000 description 1
- 230000031709 bromination Effects 0.000 description 1
- 238000005893 bromination reaction Methods 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 150000001804 chlorine Chemical class 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 150000001924 cycloalkanes Chemical group 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- SKSVCKGZZUFGGC-UHFFFAOYSA-N n-methylmethanamine;propanoic acid Chemical compound C[NH2+]C.CCC([O-])=O SKSVCKGZZUFGGC-UHFFFAOYSA-N 0.000 description 1
- LQNUZADURLCDLV-IDEBNGHGSA-N nitrobenzene Chemical group [O-][N+](=O)[13C]1=[13CH][13CH]=[13CH][13CH]=[13CH]1 LQNUZADURLCDLV-IDEBNGHGSA-N 0.000 description 1
- 229950010765 pivalate Drugs 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 238000007348 radical reaction Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
Classifications
-
- 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
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B39/00—Halogenation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
- C07C17/15—Preparation of halogenated hydrocarbons by replacement by halogens with oxygen as auxiliary reagent, e.g. oxychlorination
- C07C17/152—Preparation of halogenated hydrocarbons by replacement by halogens with oxygen as auxiliary reagent, e.g. oxychlorination of hydrocarbons
- C07C17/154—Preparation of halogenated hydrocarbons by replacement by halogens with oxygen as auxiliary reagent, e.g. oxychlorination of hydrocarbons of saturated hydrocarbons
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
- C07C17/15—Preparation of halogenated hydrocarbons by replacement by halogens with oxygen as auxiliary reagent, e.g. oxychlorination
- C07C17/158—Preparation of halogenated hydrocarbons by replacement by halogens with oxygen as auxiliary reagent, e.g. oxychlorination of halogenated hydrocarbons
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C231/00—Preparation of carboxylic acid amides
- C07C231/12—Preparation of carboxylic acid amides by reactions not involving the formation of carboxamide groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/30—Preparation of carboxylic acid nitriles by reactions not involving the formation of cyano groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/347—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups
- C07C51/363—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups by introduction of halogen; by substitution of halogen atoms by other halogen atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/28—Preparation of carboxylic acid esters by modifying the hydroxylic moiety of the ester, such modification not being an introduction of an ester group
- C07C67/287—Preparation of carboxylic acid esters by modifying the hydroxylic moiety of the ester, such modification not being an introduction of an ester group by introduction of halogen; by substitution of halogen atoms by other halogen atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
- C07C67/307—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by introduction of halogen; by substitution of halogen atoms by other halogen atoms
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a preparation method of alkane chloride, which uses air or oxygen as an oxidant, uses a chlorine-containing compound as the alkane chloride, adds the chlorine-containing compound represented by sodium chloride, a substituent source, alkane, a catalyst or an oxidant and acid into a solvent, adds the solvent into a light-transmitting reaction vessel under the atmosphere of air or oxygen, seals the reaction vessel, stirs the reaction vessel under the conditions of normal pressure and illumination, and obtains the alkane chloride or an ester through analyzing nuclear magnetic yield, extracting, drying and filtering. Compared with the prior art, the invention utilizes cheap and safe chlorine-containing compounds represented by sodium chloride as a chlorine source or a catalyst, can react under the conditions of air normal temperature and normal pressure and containing water, and has the advantages of energy saving, economy, convenient and safe operation and environmental friendliness.
Description
Technical Field
The invention relates to the technical field of chemical industry, in particular to a preparation method of alkane chloride.
Background
The alkane substitute is an important organic chemical, wherein alkane chloride and ester substitute alkane are mainly used as solvents of organic materials and medicines, and bromoalkane is mainly used as an intermediate to be applied to synthesis of various organic materials, medicines and daily necessities. The common alkane is activated to prepare alkane chloride, usually the radical reaction of alkane is adopted, and the reaction is mainly the chlorination reaction with high efficiency, wherein the chlorine source is mainly chlorine gas or chlorine reagent with high valence state (such as NCS). Chlorine (Cl) 2 ) The utilization of chlorine is usually not more than 50 percent, because the equivalent HCl byproduct is generated by the reaction, and chlorine is a highly toxic gas, so the production process has large pollution, and is inconvenient to store, transport and use and very dangerous. The chlorine reagent is not only complex in synthesis, but also poor in atom economy. In addition, in order to improve the utilization rate of chlorine and make the operation more convenient, people also try to use chlorine anions combined with an oxidant as a chlorine source, but the chlorine ions are oxidized to chlorine gas with the standard electrode potential as high as 1.358 volts, and the reactions discovered before are generally more severe in reaction conditions and poor in product selectivity. Wherein the oxidant is high-valence metal ion, sodium hypochlorite, H 2 O 2 Oxone, and the like.
H 2 O 2 Is the greenest oxidizing agent in the reactions reported so far, since its by-product is only water. In 2008, Srinivas et al reported the use of mesoporous molecular sieve SBA-15, hydrochloric acid as the chlorine source, H 2 O 2 Is used as oxidant and is reacted at room temperature in acid system. The reaction chlorine source and the oxidant both need to be excessively added, and the dosage of the molecular sieve is also larger [ Srinivas, D.; saikia, L.Catal.Surv.Asia 2008,12,114]。
A part of the prior art disclosed in 2017 reports that chlorination of alkane can be realized at room temperature under the condition of common illumination by using sodium chloride as a chlorine source and adding an oxidant. [ Zhao, m.; lu, W.org.Lett.2017,19, 4560-
The conversion of chlorine atoms in this technique is extremely high, but it still requires the addition of the previously prepared oxidant Oxone, and the use of the most ideal air as oxidant cannot be used. The most desirable oxidants are oxygen and air, and alkane chlorination reactions using them as oxidants have not been reported so far.
This laboratory has disclosed a preparation method for bromo alkane in patent CN 108358748B, said method uses sodium nitrite reagent as catalyst, can produce alkane bromide under the condition that bromine anion compound is used as bromine source, air is used as oxidizing agent, said condition uses air as oxidizing agent to implement bromination substitution to alkane and substituted alkane, but said patent is mainly directed at preparation of bromo alkane product, can't obtain chloro product through said method, the invention further improves on the basis of this patent method, have realized the preparation of chloro product. Compared with other chlorination methods, the method has the advantages of direct means, short path, excellent atom economy, mild reaction conditions, simple and convenient operation and environmental friendliness.
Disclosure of Invention
The present invention aims at overcoming the demerits of available technology, and provides one kind of alkane chloride preparing process with air or oxygen as oxidant and chlorine anion compound as chlorine source. The method has the advantages of high chlorine utilization rate, mild reaction conditions, simple and convenient operation and environmental friendliness.
The purpose of the invention can be realized by the following technical scheme:
a process for preparing the chloralkane includes such steps as adding the chloralkane, chlorine-contained compound, catalyst and acid to solvent, adding the solvent to transparent reaction container in air or oxygen atmosphere, sealing, stirring while reacting under ordinary pressure and light, and adding CDCl to the mixture after reaction 3 And internal standard, drying and sampling 1 H NMR analysis to give nuclear magnetic yield using CH 2 Cl 2 Extracting, drying with anhydrous sodium sulfate, filtering, distilling the filtrate under reduced pressure to obtain crude product, and separating the crude product by column chromatography to obtain pure alkane chloride product.
The reaction can be represented by the following overall reaction equation:
the chemical structure of the alkane is shown as (I), and R-H is sp-containing 3 All alkanes of C1 to C30 of C-H bonds, including straight, branched or cyclic alkanes, or alkanes bearing one or more substituents, including nitro, carboxyl or aryl groups; such as nitropropane.
The chlorine-containing compound is a compound containing chlorine anions and comprises hydrogen chloride and chlorine-containing metal salt, or quaternary ammonium salt containing the chlorine anions or resin and silica gel loaded with the chlorine anions;
the catalyst is a nitrogen-containing catalyst and comprises nitric acid, nitrous acid, nitrate and nitrite, and nitrogen oxides comprise NO and NO 2 Quaternary ammonium salts containing nitrate or nitrite, or resins and other supporting materials loaded with nitrate, nitrite or nitrogen oxide;
the acids include all protic acids.
The molar weight of the alkane is 50 to 100 times of that of the chlorine-containing compound; the mol weight of the nitrogen-containing reagent catalyst is 0.1 to 300 percent of that of the chlorine-containing compound; the molar amount of the acid is 100 to 500 percent of the chlorine-containing compound or chlorine.
The solvent is an acidic solvent or a neutral solvent.
The acidic solvent is CF 3 CH 2 OH or organic acid, and the neutral solvent is CH 3 NO 2 ,Ph NO 2 ,MeCN,CH 2 Cl 2 Or CHCl 3 . The reaction may also be carried out without addition of a solvent.
The illumination condition is natural light or an external light source, the reaction can be accelerated and the continuity of the reaction can be ensured by properly adding the light source, and the external light source can adopt an incandescent lamp, a straight fluorescent lamp, a compact fluorescent lamp, an LED lamp or an ultraviolet lamp, and the power is more than 4W.
The reaction temperature is controlled to be-5 to 50 ℃, and the reaction time is controlled to be 2 to 48 hours.
The obtained alkane chloride is sp of alkane 3 Monochloride and partial dichloride of C-H bonds.
Compared with the prior art, the invention has the following advantages:
(1) chlorinated alkanes which require more drastic or toxic and harmful production conditions are obtained in a more selective manner in a milder manner.
(2) The synthetic route is short, and the raw materials are simple and cheap.
(3) Chlorine salt (such as NaCl) which is convenient to store and transport can be used as a chlorine source, so that the use of common chlorine is avoided, a large amount of harmful gas cannot be generated, the utilization rate of chlorine atoms is high, and the chlorine-free chlorine storage tank is economic and environment-friendly;
(4) air is used as the final oxidant, so that the cost is greatly reduced, and the method is suitable for being popularized to industrialization;
(5) using nitrogen-containing reagents (e.g. NaNO) 2 ) As catalyst, compared with the commonly used metal catalyst, the price is extremely lowEasy to obtain, low in toxicity and convenient to treat;
(6) the light source used in the reaction is visible light (such as natural light), and a special light source (such as ultraviolet light) is not needed;
(7) the reaction can be carried out under the conditions of normal temperature and normal pressure, the reaction reagent does not need to be dehydrated in advance, a reaction system does not need to be protected by water in the reaction process, and the energy-saving and economic effects are achieved. In a word, the reaction raw materials are cheap and easy to obtain, the operation is convenient and safe, and the method is environment-friendly.
Detailed Description
The present invention will be described in detail with reference to specific examples. The following examples will assist those skilled in the art in further understanding the invention, but are not intended to limit the invention in any way. It should be noted that variations and modifications can be made by persons skilled in the art without departing from the spirit of the invention. All falling within the scope of the present invention.
Example 1
The magneton was added to the tube, sodium chloride (0.5mmol,4eq), sodium nitrite (0.0125mmol,0.1eq), nitropropane (0.125mmol,1eq), nitromethane (0.1L), methanesulfonic acid (0.5mmol,4eq) were added in sequence, and after the tube was sealed, a 23 watt LED lamp was used 3 cm from the tube, and the tube was stirred and illuminated. The reaction is terminated with CDCl 3 1mL of the diluted solution was added with 0.5g of anhydrous sodium sulfate and a quantitative internal standard CH 2 Br 2 Stirring for 30 seconds, precipitating for 10 minutes, and collecting about 500L of supernatant 1 H NMR detected and calculated yield.
This example illustrates a reaction at room temperature with nitromethane as the solvent, nitropropane, air and sodium chloride as the starting materials, nitrite as the catalyst, methane in an amount of 10% of the input, methanesulfonic acid as the acid, and a 23 watt LED energy-saving lamp as the light source.
Example 2
And adding magnetons into the sealed tube, sequentially adding sodium nitrite (0.0125mmol,0.1eq), nitropropane (0.125mmol,1eq), nitromethane (0.1L) and hydrochloric acid (0.5mmol,4eq), sealing the tube, using a 23 watt LED lamp at a distance of 3 cm from the tube, and stirring and illuminating. The reaction is terminated with CDCl 3 1mL of the diluted solution was added with 0.5g of anhydrous sodium sulfate and a quantitative internal standard CH 2 Br 2 Stirring for 30 seconds, precipitating for 10 minutes, and collecting about 500L of supernatant 1 HNMR was examined and the yield was calculated.
This example illustrates the reaction of a chlorine source with an acid which is hydrochloric acid.
Example 3
The tube was sealed and magnetons were added, followed by sodium nitrite (0.0125mmol,0.1eq), nitropropane (0.125mmol,1eq), dichloromethane (0.1L), hydrochloric acid (0.5mmol,4eq) in that order, and after the tube was sealed, a 23 watt LED lamp was used at a distance of 3 cm from the tube, and the tube was stirred and illuminated. The reaction is terminated with CDCl 3 1mL of the diluted solution was added with 0.5g of anhydrous sodium sulfate and a quantitative internal standard CH 2 Br 2 Stirring for 30 seconds, precipitating for 10 minutes, and collecting about 500L of supernatant 1 HNMR was examined and the yield was calculated.
This example illustrates the reaction of a chlorine source with an acid such as hydrochloric acid and a solvent such as methylene chloride.
Example 4
A magneton was added to the tube, sodium chloride (0.5mmol,4eq), sodium nitrite (0.0125mmol,0.1eq), nitropropane (0.125mmol,1eq), nitrobenzene (0.1L), methanesulfonic acid (0.5mmol,4eq) were added in sequence, and after the tube was sealed, a 23 watt LED lamp was used 3 cm from the tube, and the tube was stirred and illuminated. The reaction is terminated with CDCl 3 1mL of the diluted solution was added with 0.5g of anhydrous sodium sulfate and a quantitative internal standard CH 2 Br 2 Stirring for 30 s, precipitating for 10 min, and collecting about 500L of supernatant 1 H NMR detected and calculated yield.
This example illustrates the reaction when the solvent is nitrobenzene.
Example 5
The magneton was added to the tube, sodium chloride (0.5mmol,4eq), sodium nitrite (0.0125mmol,0.1eq), nitropropane (0.125mmol,1eq), acetonitrile (0.1L), methanesulfonic acid (0.5mmol,4eq) were added in order, and after the tube was sealed, a 23 watt LED lamp was used at a distance of 3 cm from the tube, and the tube was stirred and illuminated. The reaction is terminated with CDCl 3 1mL of the diluted solution was added with 0.5g of anhydrous sodium sulfate and a quantitative internal standard CH 2 Br 2 Stirring for 30 seconds, precipitating for 10 minutes, and collecting about 500L of supernatant 1 H NMR detected and calculated yield.
This example illustrates the reaction when the solvent is acetonitrile.
Example 6
The magneton was added to the tube, sodium chloride (0.5mmol,4eq), sodium nitrite (0.0125mmol,0.1eq), nitropropane (0.125mmol,1eq), acetic acid (0.1L), methanesulfonic acid (0.5mmol,4eq) were added in sequence, and after the tube was sealed, a 23 watt LED lamp was used at a distance of 3 cm from the tube, and the tube was stirred and illuminated. The reaction is terminated with CDCl 3 1mL of the diluted solution was added with 0.5g of anhydrous sodium sulfate and a quantitative internal standard CH 2 Br 2 Stirring for 30 seconds, precipitating for 10 minutes, and collecting about 500L of supernatant 1 H NMR detected and calculated yield.
This example illustrates the reaction when the solvent is acetic acid.
Example 7
Adding magneton into the sealed tube, and sequentially adding sodium chloride (0.5mmol,4eq) and sodium chlorideSodium nitrate (0.0125mmol,0.1eq), nitropropane (0.125mmol,1eq), trifluoroacetic acid (0.1L), methanesulfonic acid (0.5mmol,4eq), sealing the tube, using a 23 watt LED lamp 3 cm from the tube, stirring and illuminating. The reaction is terminated with CDCl 3 1mL of the diluted solution was added with 0.5g of anhydrous sodium sulfate and a quantitative internal standard CH 2 Br 2 Stirring for 30 seconds, precipitating for 10 minutes, and collecting about 500L of supernatant 1 H NMR detected and calculated yield.
This example illustrates the reaction when the solvent is trifluoroacetic acid.
Example 8
The magneton was added to the tube, sodium chloride (0.5mmol,4eq), sodium nitrite (0.0125mmol,0.1eq), nitroethane (0.125mmol,1eq), nitromethane (0.1L), methanesulfonic acid (0.5mmol,4eq) were added in order, and after the tube was sealed, a 23 watt LED lamp was used 3 cm from the tube, and the tube was stirred and illuminated. The reaction is terminated with CDCl 3 1mL of the diluted solution was added with 0.5g of anhydrous sodium sulfate and a quantitative internal standard CH 2 Br 2 Stirring for 30 seconds, precipitating for 10 minutes, and collecting about 500L of supernatant 1 H NMR detected and calculated yield.
This example illustrates the reaction when the starting material is nitroethane.
Example 9
The magneton was added to the tube, sodium chloride (0.5mmol,4eq), sodium nitrite (0.0125mmol,0.1eq), methyl propionate (0.125mmol,1eq), nitromethane (0.1L), methanesulfonic acid (0.5mmol,4eq) were added in order, and after the tube was sealed, a 23 watt LED lamp was used 3 cm from the tube, and the tube was stirred and illuminated. The reaction is terminated with CDCl 3 1mL of the diluted solution was added with 0.5g of anhydrous sodium sulfate and a quantitative internal standard CH 2 Br 2 Stirring for 30 seconds, precipitating for 10 minutes, and collecting about 500L of supernatant 1 H NMR detected and calculated yield.
This example illustrates the reaction when the starting material is methyl propionate.
Example 10
The magneton was added to the tube, sodium chloride (0.5mmol,4eq), sodium nitrite (0.0125mmol,0.1eq), propionic acid (0.125mmol,1eq), nitromethane (0.1L), methanesulfonic acid (0.5mmol,4eq) were added in order, and after the tube was sealed, a 23 watt LED lamp was used at a distance of 3 cm from the tube, and the tube was stirred and illuminated. The reaction is terminated with CDCl 3 1mL of the diluted solution was added with 0.5g of anhydrous sodium sulfate and a quantitative internal standard CH 2 Br 2 Stirring for 30 seconds, precipitating for 10 minutes, and collecting about 500L of supernatant 1 H NMR check and calculate yield.
This example illustrates the reaction when the starting material is propionic acid.
Example 11
The magneton was added to the tube, sodium chloride (0.5mmol,4eq), sodium nitrite (0.0125mmol,0.1eq), alanine amine (0.125mmol,1eq), nitromethane (0.1L), methanesulfonic acid (0.5mmol,4eq) were added in order, and after the tube was sealed, a 23 watt LED lamp was used 3 cm from the tube, and the tube was stirred and illuminated. The reaction is finished with CDCl 3 1mL of the diluted solution was added with 0.5g of anhydrous sodium sulfate and a quantitative internal standard CH 2 Br 2 Stirring for 30 seconds, precipitating for 10 minutes, and collecting about 500L of supernatant 1 H NMR check and calculate yield.
This example illustrates the reaction when the starting material is alanine amine.
Example 12
Adding magneton, sodium chloride (0.5mmol,4eq), sodium nitrite (0.0125mmol,0.1eq), dimethyl alanine amine (0.125mmol,1eq), nitromethane (0.1L), methanesulfonic acid (0.5mmol,4eq) in sequence, sealing the tubeThen, a 23 watt LED lamp is used to be 3 cm away from the tube, and the stirring illumination is carried out. The reaction is terminated with CDCl 3 1mL of the diluted solution was added with 0.5g of anhydrous sodium sulfate and a quantitative internal standard CH 2 Br 2 Stirring for 30 seconds, precipitating for 10 minutes, and collecting about 500L of supernatant 1 H NMR detected and calculated yield.
This example illustrates the reaction when the starting material is dimethyl ammonium propionate.
Example 13
The magneton was added to the tube, sodium chloride (0.5mmol,4eq), sodium nitrite (0.0125mmol,0.1eq), nitrotert-butane (0.125mmol,1eq), nitromethane (0.1L), methanesulfonic acid (0.5mmol,4eq) were added in order, and after the tube was sealed, a 23 watt LED lamp was used 3 cm from the tube, and the tube was stirred and illuminated. The reaction is terminated with CDCl 3 1mL of the diluted solution was added with 0.5g of anhydrous sodium sulfate and a quantitative internal standard CH 2 Br 2 Stirring for 30 seconds, precipitating for 10 minutes, and collecting about 500L of supernatant 1 H NMR detected and calculated yield.
This example illustrates the reaction when the starting material is nitrotert-butane.
Example 14
The magneton was added to the tube, sodium chloride (0.5mmol,4eq), sodium nitrite (0.0125mmol,0.1eq), cyano-tert-butane (0.125mmol,1eq), nitromethane (0.1L), methanesulfonic acid (0.5mmol,4eq) were added in order, and after the tube was sealed, a 23 watt LED lamp was used 3 cm from the tube, and the tube was stirred and illuminated. The reaction is terminated with CDCl 3 1mL of the diluted solution was added with 0.5g of anhydrous sodium sulfate and a quantitative internal standard CH 2 Br 2 Stirring for 30 seconds, precipitating for 10 minutes, and collecting about 500L of supernatant 1 H NMR check and calculate yield.
This example illustrates the reaction when the starting material is cyano-tert-butane.
Example 15
The magneton was added to the tube, sodium chloride (0.5mmol,4eq), sodium nitrite (0.0125mmol,0.1eq), chlorotert-butane (0.125mmol,1eq), nitromethane (0.1L), methanesulfonic acid (0.5mmol,4eq) were added in order, and after the tube was sealed, a 23 watt LED lamp was used 3 cm from the tube, and the tube was stirred and illuminated. The reaction is terminated with CDCl 3 1mL of the diluted solution was added with 0.5g of anhydrous sodium sulfate and a quantitative internal standard CH 2 Br 2 Stirring for 30 seconds, precipitating for 10 minutes, and collecting about 500L of supernatant 1 H NMR detected and calculated yield.
This example illustrates the reaction when the starting material is tert-butyl chloride.
Example 16
The magneton was added to the tube, sodium chloride (0.5mmol,4eq), sodium nitrite (0.0125mmol,0.1eq), pivalic acid (0.125mmol,1eq), nitromethane (0.1L), methanesulfonic acid (0.5mmol,4eq) were added in order, and after the tube was sealed, a 23 watt LED lamp was used 3 cm from the tube, and the tube was stirred and illuminated. The reaction is terminated with CDCl 3 1mL of the diluted solution was added with 0.5g of anhydrous sodium sulfate and a quantitative internal standard CH 2 Br 2 Stirring for 30 seconds, precipitating for 10 minutes, and collecting about 500L of supernatant 1 H NMR check and calculate yield.
This example illustrates the reaction when the starting material is pivalic acid.
Example 17
The magneton was added to the tube, sodium chloride (0.5mmol,4eq), sodium nitrite (0.0125mmol,0.1eq), ammonium pivalate (0.125mmol,1eq), nitromethane (0.1L), methanesulfonic acid (0.5mmol,4eq) were added in order, and after the tube was sealed, a 23 watt LED lamp was used 3 cm from the tube, and the tube was stirred and illuminated. The reaction is terminated with CDCl 3 1mL of the diluted solution was added with 0.5g of anhydrous sodium sulfate and a quantitative internal standard CH 2 Br 2 Stirring for 30 seconds, precipitating for 10 minutes, and collecting about 500L of supernatant 1 H NMR detected and calculated yield.
This example illustrates the reaction when the starting material is amine pivalate.
Example 18
Premixed methane with oxygen as 2:1 gas. Sodium nitrite (0.023mmol) is added into a Schlenk tube, vacuum pumping is carried out, 35mL of mixed gas is added into the Schlenk tube after ventilation, 37 percent hydrochloric acid (1.91mmol) and trifluoroacetic acid (0.7mL) are sequentially added, then a screw is screwed, and a 23-watt white LED lamp is used for illumination and stirring at a distance of 1 cm from the reactor. After the reaction was complete, 10mL of CDCl was added 3 After sufficiently shaking, adding quantitative internal standard nitromethane, stirring for 30 seconds, adding 0.5g of anhydrous sodium sulfate, precipitating for 10 minutes, and taking about 500L of supernatant 1 H NMR detected and calculated yield.
This example illustrates a reaction in which the reaction temperature is room temperature, the solvent is trifluoroacetic acid, the raw materials are methane, oxygen and hydrochloric acid, the catalyst is nitrite, the charge amount is 0.2% of methane, and the acid is hydrochloric acid.
The embodiments described above are described to facilitate an understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.
Claims (10)
1. A preparation method of alkane chloride is characterized in that a chlorine-containing compound, alkane, a catalyst and acid are added into a solvent, the solvent is added into a light-transmitting reaction container under the atmosphere of air or oxygen, the container is sealed and stirred to react under the conditions of normal pressure and illumination, and then the alkane chloride is obtained through analysis of nuclear magnetic yield, extraction, drying, filtration, reduced pressure distillation and column layer separation;
wherein the chlorine-containing compound is a compound containing chlorine anions and comprises hydrogen chloride and chlorine-containing metal salt, or quaternary ammonium salt containing the chlorine anions, or resin and silica gel loaded with the chlorine anions.
2. The method of claim 1, wherein the alkane is sp-containing 3 C-H bonded C1 to C30 alkanes.
3. The method of claim 1, wherein the molar amount of the alkane is 25 to 100 times that of the chlorine-containing compound; the molar amount of the acid is 50 to 200 percent of that of the chlorine-containing compound.
4. The method of claim 1, wherein the catalyst is a nitrogen-containing catalyst comprising nitric acid, nitrous acid, nitrate, nitrite, nitrogen oxides comprising NO, NO 2 A quaternary ammonium salt containing nitrate or nitrite, or a resin carrying nitrate, nitrite or nitrogen oxide, and other carrying materials.
5. The method of claim 1, wherein the acid is a protic acid.
6. The method according to claim 1, wherein the lighting condition is natural light or an external light source, and the external light source is an incandescent lamp, a straight fluorescent lamp, a compact fluorescent lamp, an LED lamp or an ultraviolet lamp, and the power is 4W or more.
7. The method for producing an alkane chloride as claimed in claim 1, wherein the reaction temperature is controlled to-5 to 50 ℃.
8. The method for producing an alkane chloride as claimed in claim 1, wherein the reaction time is controlled to 2 to 72 hours.
9. The method of claim 1, wherein the solvent is an acidic solvent or a neutral solvent, and the acidic solvent is CF 3 CH 2 OH or organic acid, and the neutral solvent is CH 3 NO 2 ,PhNO 2 ,MeCN,CH 2 Cl 2 Or CHCl 3 。
10. The method of claim 1, wherein the substituted alkane is sp of alkane 3 A C-H bond.
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Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
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GB1254248A (en) * | 1969-07-03 | 1971-11-17 | Gulf Research Development Co | A process for preparing chlorinated and brominated aromatic compounds |
CN108358748A (en) * | 2018-03-28 | 2018-08-03 | 上海交通大学 | A kind of preparation method of alkane bromo-derivative |
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Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
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GB1254248A (en) * | 1969-07-03 | 1971-11-17 | Gulf Research Development Co | A process for preparing chlorinated and brominated aromatic compounds |
CN108358748A (en) * | 2018-03-28 | 2018-08-03 | 上海交通大学 | A kind of preparation method of alkane bromo-derivative |
Non-Patent Citations (2)
Title |
---|
MENGDI ZHAO AND WENJUN LU: "Visible Light-Induced Oxidative Chlorination of Alkyl sp3 C−H Bonds with NaCl/Oxone at Room Temperature" * |
赵梦迪: "可见光驱动的烷烃sp3C-H键氧化氯代和溴代反应" * |
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