JP2002030044A - Method for producing tetraalkylammonium halide - Google Patents
Method for producing tetraalkylammonium halideInfo
- Publication number
- JP2002030044A JP2002030044A JP2000210627A JP2000210627A JP2002030044A JP 2002030044 A JP2002030044 A JP 2002030044A JP 2000210627 A JP2000210627 A JP 2000210627A JP 2000210627 A JP2000210627 A JP 2000210627A JP 2002030044 A JP2002030044 A JP 2002030044A
- Authority
- JP
- Japan
- Prior art keywords
- solvent
- tetraalkylammonium halide
- carbon atoms
- reaction
- general formula
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- -1 tetraalkylammonium halide Chemical class 0.000 title claims abstract description 27
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 27
- 239000002904 solvent Substances 0.000 claims abstract description 22
- 239000000010 aprotic solvent Substances 0.000 claims abstract description 10
- 150000002148 esters Chemical class 0.000 claims abstract description 3
- 150000002576 ketones Chemical class 0.000 claims abstract description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical group CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- 150000008282 halocarbons Chemical class 0.000 claims description 6
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 5
- 238000009835 boiling Methods 0.000 claims description 5
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 5
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 claims description 4
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- XJWSAJYUBXQQDR-UHFFFAOYSA-M dodecyltrimethylammonium bromide Chemical compound [Br-].CCCCCCCCCCCC[N+](C)(C)C XJWSAJYUBXQQDR-UHFFFAOYSA-M 0.000 claims description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 2
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- 239000002244 precipitate Substances 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims 8
- 125000002723 alicyclic group Chemical group 0.000 claims 4
- 150000001875 compounds Chemical class 0.000 claims 4
- 125000001931 aliphatic group Chemical group 0.000 claims 3
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 claims 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 claims 1
- 125000003118 aryl group Chemical group 0.000 claims 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical group BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims 1
- 229910052794 bromium Chemical group 0.000 claims 1
- 229910052801 chlorine Inorganic materials 0.000 claims 1
- 239000000460 chlorine Substances 0.000 claims 1
- 125000001309 chloro group Chemical group Cl* 0.000 claims 1
- 229910052736 halogen Inorganic materials 0.000 claims 1
- 150000002367 halogens Chemical group 0.000 claims 1
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 1
- 239000013078 crystal Substances 0.000 abstract description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract description 6
- 238000001035 drying Methods 0.000 abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 4
- 150000002170 ethers Chemical class 0.000 abstract description 2
- 239000007810 chemical reaction solvent Substances 0.000 abstract 1
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 14
- 239000002002 slurry Substances 0.000 description 13
- 239000000243 solution Substances 0.000 description 12
- 238000010992 reflux Methods 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 8
- 239000002994 raw material Substances 0.000 description 8
- 238000001914 filtration Methods 0.000 description 7
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 238000004809 thin layer chromatography Methods 0.000 description 5
- PBLNBZIONSLZBU-UHFFFAOYSA-N 1-bromododecane Chemical compound CCCCCCCCCCCCBr PBLNBZIONSLZBU-UHFFFAOYSA-N 0.000 description 4
- 230000008034 disappearance Effects 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000003586 protic polar solvent Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 150000003512 tertiary amines Chemical class 0.000 description 4
- 239000012298 atmosphere Substances 0.000 description 3
- 239000012267 brine Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000001953 recrystallisation Methods 0.000 description 3
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 3
- QPUYECUOLPXSFR-UHFFFAOYSA-N 1-methylnaphthalene Chemical compound C1=CC=C2C(C)=CC=CC2=C1 QPUYECUOLPXSFR-UHFFFAOYSA-N 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- VFWCMGCRMGJXDK-UHFFFAOYSA-N 1-chlorobutane Chemical compound CCCCCl VFWCMGCRMGJXDK-UHFFFAOYSA-N 0.000 description 1
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- SVYKKECYCPFKGB-UHFFFAOYSA-N N,N-dimethylcyclohexylamine Chemical compound CN(C)C1CCCCC1 SVYKKECYCPFKGB-UHFFFAOYSA-N 0.000 description 1
- GSCCALZHGUWNJW-UHFFFAOYSA-N N-Cyclohexyl-N-methylcyclohexanamine Chemical compound C1CCCCC1N(C)C1CCCCC1 GSCCALZHGUWNJW-UHFFFAOYSA-N 0.000 description 1
- MKYQPGPNVYRMHI-UHFFFAOYSA-N Triphenylethylene Chemical group C=1C=CC=CC=1C=C(C=1C=CC=CC=1)C1=CC=CC=C1 MKYQPGPNVYRMHI-UHFFFAOYSA-N 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 239000003899 bactericide agent Substances 0.000 description 1
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 description 1
- 229940073608 benzyl chloride Drugs 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- KXHPPCXNWTUNSB-UHFFFAOYSA-M benzyl(trimethyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CC1=CC=CC=C1 KXHPPCXNWTUNSB-UHFFFAOYSA-M 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- BMDRYIFEJILWIP-UHFFFAOYSA-M butyl(triethyl)azanium;chloride Chemical compound [Cl-].CCCC[N+](CC)(CC)CC BMDRYIFEJILWIP-UHFFFAOYSA-M 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 125000004210 cyclohexylmethyl group Chemical group [H]C([H])(*)C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C1([H])[H] 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000002140 halogenating effect Effects 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- JDEJGVSZUIJWBM-UHFFFAOYSA-N n,n,2-trimethylaniline Chemical compound CN(C)C1=CC=CC=C1C JDEJGVSZUIJWBM-UHFFFAOYSA-N 0.000 description 1
- YQYUUNRAPYPAPC-UHFFFAOYSA-N n,n-diethyl-2-methylaniline Chemical compound CCN(CC)C1=CC=CC=C1C YQYUUNRAPYPAPC-UHFFFAOYSA-N 0.000 description 1
- AJUXDFHPVZQOGF-UHFFFAOYSA-N n,n-dimethyl-1-naphthylamine Chemical compound C1=CC=C2C(N(C)C)=CC=CC2=C1 AJUXDFHPVZQOGF-UHFFFAOYSA-N 0.000 description 1
- YWFWDNVOPHGWMX-UHFFFAOYSA-N n,n-dimethyldodecan-1-amine Chemical compound CCCCCCCCCCCCN(C)C YWFWDNVOPHGWMX-UHFFFAOYSA-N 0.000 description 1
- UQKAOOAFEFCDGT-UHFFFAOYSA-N n,n-dimethyloctan-1-amine Chemical compound CCCCCCCCN(C)C UQKAOOAFEFCDGT-UHFFFAOYSA-N 0.000 description 1
- XTAZYLNFDRKIHJ-UHFFFAOYSA-N n,n-dioctyloctan-1-amine Chemical compound CCCCCCCCN(CCCCCCCC)CCCCCCCC XTAZYLNFDRKIHJ-UHFFFAOYSA-N 0.000 description 1
- UWHRNIXHZAWBMF-UHFFFAOYSA-N n-dodecyl-n-methyldodecan-1-amine Chemical compound CCCCCCCCCCCCN(C)CCCCCCCCCCCC UWHRNIXHZAWBMF-UHFFFAOYSA-N 0.000 description 1
- XWCCTMBMQUCLSI-UHFFFAOYSA-N n-ethyl-n-propylpropan-1-amine Chemical compound CCCN(CC)CCC XWCCTMBMQUCLSI-UHFFFAOYSA-N 0.000 description 1
- XVWQQNARVMHZBP-UHFFFAOYSA-N n-methyl-2-phenyl-n-(2-phenylethyl)ethanamine Chemical compound C=1C=CC=CC=1CCN(C)CCC1=CC=CC=C1 XVWQQNARVMHZBP-UHFFFAOYSA-N 0.000 description 1
- DYFFAVRFJWYYQO-UHFFFAOYSA-N n-methyl-n-phenylaniline Chemical compound C=1C=CC=CC=1N(C)C1=CC=CC=C1 DYFFAVRFJWYYQO-UHFFFAOYSA-N 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000003444 phase transfer catalyst Substances 0.000 description 1
- 125000000286 phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004344 phenylpropyl group Chemical group 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 239000003507 refrigerant Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000013076 target substance Substances 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- SWZDQOUHBYYPJD-UHFFFAOYSA-N tridodecylamine Chemical compound CCCCCCCCCCCCN(CCCCCCCCCCCC)CCCCCCCCCCCC SWZDQOUHBYYPJD-UHFFFAOYSA-N 0.000 description 1
- ODHXBMXNKOYIBV-UHFFFAOYSA-N triphenylamine Chemical compound C1=CC=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 ODHXBMXNKOYIBV-UHFFFAOYSA-N 0.000 description 1
- 125000002221 trityl group Chemical group [H]C1=C([H])C([H])=C([H])C([H])=C1C([*])(C1=C(C(=C(C(=C1[H])[H])[H])[H])[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明はハロゲン化炭化水素と３
級アミンを非プロトン性溶媒中で反応させ、析出するテ
トラアルキルアンモニウムハライドを分離・精製するこ
とにより、高収率、高純度で目的とするテトラアルキル
アンモニウムハライドを製造する方法に関する。テトラ
アルキルアンモニウムハライドはイオン性と親水性・親
油性の両性を併せ持つことから、カチオン活性剤として
樹脂の帯電防止剤、導電性付与剤などに用いられてお
り、有機合成時の相間移動触媒として有用な物質であ
る。また、エポキシ樹脂やポリオレフィン樹脂の重合触
媒として、更に、ハロゲン化剤や酸化剤、防菌剤、水処
理剤など利用分野は多岐にわたる。This invention relates to halogenated hydrocarbons and 3
The present invention relates to a method for producing a desired tetraalkylammonium halide with high yield and high purity by reacting a secondary amine in an aprotic solvent and separating and purifying the precipitated tetraalkylammonium halide. Because tetraalkylammonium halides have both ionic, hydrophilic and lipophilic properties, they are used as cation activators in antistatic agents and conductivity imparting agents for resins, and are useful as phase transfer catalysts during organic synthesis. Substance. Further, as a polymerization catalyst for an epoxy resin or a polyolefin resin, there are a wide variety of application fields such as a halogenating agent, an oxidizing agent, a bactericide, and a water treatment agent.
【０００２】[0002]
【従来の技術】テトラアルキルアンモニウムハライドは
イオン反応により合成されるため一般的にはプロトン性
溶媒である水や低級アルコール中で速やかに反応する。
これらの溶媒を単独又は混合して用い、常圧もしくは加
圧下で反応を行うことが一般に知られている。例えば、
Journal of American Chemical Society vol.６５.６９
３、特開平１０-２８７６３０、特開平１１-２７９１３
３、などに製造方法が記されている。2. Description of the Related Art Since tetraalkylammonium halides are synthesized by an ionic reaction, they generally react quickly in water or a lower alcohol which is a protic solvent.
It is generally known that these solvents are used alone or as a mixture and the reaction is carried out under normal pressure or under pressure. For example,
Journal of American Chemical Society vol.65.69
3, JP-A-10-287630, JP-A-11-27913
3, etc. describe the manufacturing method.
【０００３】しかし上記の方法では、テトラアルキルア
ンモニウムハライドのプロトン性溶媒への溶解度が高い
ので、溶媒を除去し目的物を分離精製するには低温再結
晶するか溶媒を蒸発させて固体化する必要がある。However, in the above method, the tetraalkylammonium halide has a high solubility in a protic solvent. Therefore, in order to remove the solvent and separate and purify the desired product, it is necessary to recrystallize at low temperature or evaporate the solvent to solidify. There is.
【０００４】低温再結晶を行う場合、１回の再結晶で回
収される量が少なく、濃縮・再結晶・分離の工程を繰り
返さなければならないため、生産効率が著しく低く、収
率も低下する。また、テトラアルキルアンモニウムハラ
イドはプロトン性溶媒を吸着しやすい性質があるので、
結晶を分離精製する際、大気中の水分が吸着し潮解性を
帯び、取り扱いが困難となり乾燥にも時間がかかる。When low-temperature recrystallization is performed, the amount recovered in one recrystallization is small, and the steps of concentration, recrystallization, and separation must be repeated, so that the production efficiency is extremely low and the yield is low. In addition, since tetraalkylammonium halide has a property of easily adsorbing a protic solvent,
When separating and refining crystals, moisture in the atmosphere is adsorbed and deliquescent, handling becomes difficult, and drying takes time.
【０００５】一方、溶媒を蒸発させ固体化する際は蒸発
乾固用の特殊な装置が必要になるばかりではなく、未反
応の原料を含んだ粗結晶が得られるため、純度の低い製
品となり、結果として再精製を行わなければならないと
いう欠点を有する。On the other hand, when the solvent is evaporated to be solidified, not only a special apparatus for evaporating to dryness is required, but also a crude crystal containing unreacted raw materials is obtained, so that the product has low purity. As a result, it has the disadvantage that repurification must be performed.
【０００６】[0006]
【発明が解決しようとする課題】テトラアルキルアンモ
ニウムハライドをほとんど溶解することのない非プロト
ン性溶媒を使用して反応を行い、溶媒に溶解することな
く析出してきたテトラアルキルアンモニウムハライドの
結晶を分離精製し、得られた結晶を室温〜反応終了物の
温度範囲内で乾燥することにより、高収率で高純度の目
的物を製造する方法を提供する。The reaction is carried out using an aprotic solvent which hardly dissolves the tetraalkylammonium halide, and the crystals of the tetraalkylammonium halide precipitated without being dissolved in the solvent are separated and purified. The present invention provides a method for producing a high-purity target product in a high yield by drying the obtained crystals in a temperature range from room temperature to the end of the reaction.
【０００７】[0007]
【課題を解決するための手段】本発明はテトラアルキル
アンモニウムハライドを製造する際に一般に使用される
プロトン性の溶媒、例えば水や低級アルコール類を使用
することなく、テトラアルキルアンモニウムハライドの
結晶をほとんど溶解しない、しかも工業的に利用可能な
非プロトン性の溶媒中で反応することにより、簡便操作
で目的物である高純度テトラアルキルアンモニウムハラ
イドを高収率で製造する方法である。According to the present invention, almost no tetraalkylammonium halide crystals are used without using a protic solvent generally used in the production of tetraalkylammonium halides, for example, water or lower alcohols. This is a method in which a high-purity tetraalkylammonium halide, which is the target substance, is produced in a high yield by a simple operation by reacting in an industrially available aprotic solvent that does not dissolve.
【０００８】前記溶媒のうち、詳しくはエステル類とし
て酢酸エチル、酢酸ブチル、ケトン類としてはメチルエ
チルケトン、メチルイソブチルケトン、エーテル類とし
てはテトラヒドロフラン、１,４−ジオキサンなどがあ
げられる。これらの溶媒は工業的に安価で、本反応の際
には混合せずに単独で用いることが可能であり、回収し
て再利用することにより製造費用を低減することができ
る。Among the above-mentioned solvents, esters include ethyl acetate and butyl acetate, ketones include methyl ethyl ketone and methyl isobutyl ketone, and ethers include tetrahydrofuran and 1,4-dioxane. These solvents are industrially inexpensive and can be used alone without being mixed during the reaction, and the production cost can be reduced by recovering and reusing.
【０００９】原料であるハロゲン化炭化水素としては例
えばメチル、エチル、プロピル、ブチル、オクチル、デ
シル、ドデシル、テトラデシル、ヘキサデシル、オクタ
デシル、ベンジル、フェネチル、フェニルエチル、フェ
ニルプロピル、トリフェニルメチル、トリフェニルエチ
レン、メチルナフタレン、シクロヘキシルメチル、シク
ロヘキシルプロピルの塩化、臭化、ヨウ化物などがあげ
られる。Examples of the halogenated hydrocarbon as a raw material include methyl, ethyl, propyl, butyl, octyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl, benzyl, phenethyl, phenylethyl, phenylpropyl, triphenylmethyl and triphenylethylene. , Methylnaphthalene, cyclohexylmethyl, cyclohexylpropyl, chloride, bromide and iodide.
【００１０】また、もう一方の原料である３級アミンと
しては例えばトリメチルアミン、トリエチルアミン、ト
リブチルアミン、トリオクチルアミン、トリドデシルア
ミン、 N,N-ジメチルオクチルアミン、N,N-ジメチルド
デシルアミン、 N,N-ジメチルオクタドデシルアミン、
N,N-ジプロピルエチルアミン、 N,N-ジドデシルメチル
アミン、トリス２メチルアリルアミン、 N,N-ジメチル
ベンジルアミン、 N,N-ジメチルトルイジン、 N,N-ジエ
チルトルイジン、 N,N-ジメチル１ナフチルアミン、 N-
メチルジフェニルアミン、N-メチルジフェネチルアミ
ン、トリフェニルアミン、 N,N-ジメチルシクロヘキシ
ルアミン、 N,N-メチルジシクロヘキシルアミンなどが
あげられる。[0010] The tertiary amine which is the other raw material includes, for example, trimethylamine, triethylamine, tributylamine, trioctylamine, tridodecylamine, N, N-dimethyloctylamine, N, N-dimethyldodecylamine, N-dimethyloctadodecylamine,
N, N-dipropylethylamine, N, N-didodecylmethylamine, tris-2-methylallylamine, N, N-dimethylbenzylamine, N, N-dimethyltoluidine, N, N-diethyltoluidine, N, N-dimethyl1 Naphthylamine, N-
Examples include methyldiphenylamine, N-methyldiphenethylamine, triphenylamine, N, N-dimethylcyclohexylamine, N, N-methyldicyclohexylamine and the like.
【００１１】ハロゲン化炭化水素及び３級アミンの反応
モル比は１：１でよいが採算性、廃棄物処理等が問題と
ならない程度であれば、いずれか一方を０〜５０％モル
程度過剰に用いてもよい。また、溶媒の量は使用溶媒及
びテトラアルキルアンモニウムハライドの種類によって
異なるが、反応後のスラリーが十分撹拌できる程度の
量、すなはち、結晶の重量に対し２〜１０倍量を用いる
のが好ましく、できるだけ釜効率を上げるために最少量
を用いるようにする。The reaction molar ratio of the halogenated hydrocarbon and the tertiary amine may be 1: 1. However, as long as profitability, waste treatment and the like do not matter, either one of them is excessively added by about 0 to 50% by mol. May be used. The amount of the solvent varies depending on the type of the used solvent and the tetraalkylammonium halide, but it is preferable to use an amount such that the slurry after the reaction can be sufficiently stirred, that is, 2 to 10 times the weight of the crystal. In order to increase the pot efficiency as much as possible, use the minimum amount.
【００１２】本発明方法は一般に原料を溶媒に混合し徐
々に加熱することにより実施される。この時、原料のハ
ロゲン化炭化水素及び３級アミンが低沸点の場合、反応
系内からガスとして排出されないよう、必要ならコンデ
ンサに冷媒を通すなどして還流を行いながら注意深く加
熱し、最終的には溶媒の沸点まで上昇する。また、必要
なら加圧による反応も可能である。The method of the present invention is generally carried out by mixing the raw materials in a solvent and gradually heating the mixture. At this time, if the halogenated hydrocarbon and tertiary amine as the raw materials have a low boiling point, carefully heat them while refluxing by passing a refrigerant through a condenser, if necessary, so as not to be discharged as a gas from the reaction system. Rises to the boiling point of the solvent. Further, if necessary, a reaction under pressure can be performed.
【００１３】反応の進行とともに結晶が析出しスラリー
が徐々に濃くなってくる。反応の終点は反応液の沸点上
昇が停止するすることで、または、薄層クロマトグラフ
ィーによる原料のスポットが消失することにより確認で
きる。As the reaction proceeds, crystals precipitate and the slurry gradually thickens. The end point of the reaction can be confirmed by stopping the rise of the boiling point of the reaction solution or by disappearing the spot of the raw material by thin layer chromatography.
【００１４】反応の終点を確認したらスラリーの温度を
必要に応じて室温に下げ、室温〜反応終了物の沸点の範
囲内で溶媒と分離した後、必要ならば結晶の洗浄を行
う。尚、洗浄用の溶媒は回収再利用を考慮し反応に使用
した溶媒を使用することが好ましい。この際得られる結
晶の収率は、一般に理論収率の９５％以上であり、分離
した溶媒中にはほとんどテトラアルキルアンモニウムハ
ライド及び原料が含まれておらず、そのまま次の反応に
使用可能であり、必要ならば蒸留回収し再利用すること
もできる。After confirming the end point of the reaction, the temperature of the slurry is lowered to room temperature, if necessary, separated from the solvent within the range from room temperature to the boiling point of the reaction product, and the crystals are washed if necessary. In addition, it is preferable to use the solvent used for the reaction in consideration of recovery and reuse as the washing solvent. The yield of the crystals obtained at this time is generally 95% or more of the theoretical yield, and the separated solvent contains almost no tetraalkylammonium halide and raw materials, and can be used for the next reaction as it is. If necessary, it can be recovered by distillation and reused.
【００１５】結晶を分離する工程では結晶に付着する溶
媒の雰囲気により大気中の水分を吸湿することなく乾燥
工程に進むことができるため作業性が良く、また、溶媒
を含んだ結晶は大気圧以下の減圧、加熱状態で容易に乾
燥できる。In the step of separating the crystals, the workability is good because the atmosphere of the solvent adhering to the crystals allows the process to proceed to the drying step without absorbing the moisture in the atmosphere. It can be easily dried under reduced pressure and heating.
【００１６】[0016]
【実施例】以下、実施例及び比較例により本発明を詳し
く説明するが、本発明はこれら実施例のみになんら限定
されるものではない。EXAMPLES The present invention will be described in detail below with reference to examples and comparative examples, but the present invention is not limited to these examples.
【００１７】[0017]
【実施例】実施例１ ３リットル（Ｌ）４つ口フラスコに酢酸ブチル１８７５
ｇを投入し、ガス分配フィルターを通じトリメチルアミ
ンガス１４３.１ｇ（２.4２モル）を吹き込み溶解し
た。この溶液にn-ドデシルブロマイド４６４.２ｇ（１.
８６モル）を混合し撹拌を開始した。−５℃に冷却した
ブラインを通したジムロート冷却管を装着した後、オイ
ルバスにより徐々に加熱した。昇温の際には、トリメチ
ルアミンが系外に排出されないよう注意深く加熱し、昇
温開始１時間後に液温７５℃で還流が始まった。以後、
還流を続けながら徐々に昇温し、７時間で１１０℃に達
し、これ以上の温度上昇はなくなった。この間、溶液の
状態としては、昇温開始直後からスラリー化し始め、徐
々にスラリー濃度が濃くなってた。昇温開始から全８時
間後に反応液を薄層クロマトグラフィーにより分析した
結果、 n-ドデシルブロマイドの消失を確認し反応を終
了した。このスラリーを２５℃まで冷却し、濾過分離し
た結晶を少量の酢酸ブチルで洗浄した後、５０ｍｍＨｇ
の減圧下、６０℃で乾燥した結果、白色粉末であるn-ド
デシルトリメチルアンモニウムブロマイド５６９.６ｇ
を収率９９.２％で得た。元素重量分析の結果、Ｃ５８.
４１、Ｈ１１.１３、Ｎ４.５３、Br２５.９１％（ 理論
重量Ｃ５８.４３、Ｈ１１.１１、Ｎ４.５３、Br２５.９
３％）であった。EXAMPLE 1 1875 butyl acetate was placed in a 3 liter (L) four-necked flask.
Then, 143.1 g (2.42 mol) of trimethylamine gas was blown through a gas distribution filter and dissolved. To this solution was added 464.2 g of n-dodecyl bromide (1.
86 mol) and stirring was started. After installing a Dimroth condenser through which the brine was cooled to -5 ° C, the mixture was gradually heated by an oil bath. At the time of temperature rise, heating was carried out carefully so that trimethylamine was not discharged out of the system, and reflux started at a liquid temperature of 75 ° C. one hour after the start of temperature rise. Since then
The temperature was gradually increased while the reflux was continued, and reached 110 ° C. in 7 hours. During this time, the state of the solution began to be a slurry immediately after the start of the temperature rise, and the slurry concentration gradually increased. After a total of 8 hours from the start of the temperature rise, the reaction solution was analyzed by thin layer chromatography. As a result, disappearance of n-dodecyl bromide was confirmed, and the reaction was terminated. The slurry was cooled to 25 ° C., and the crystals separated by filtration were washed with a small amount of butyl acetate, and then washed with 50 mmHg.
As a result of drying at 60 ° C. under reduced pressure, 569.6 g of n-dodecyltrimethylammonium bromide as a white powder was obtained.
Was obtained in a yield of 99.2%. As a result of elemental weight analysis, C58.
41, H11.13, N4.53, Br25.91% (theoretical weight C58.43, H11.11, N4.53, Br25.9
3%).
【００１８】実施例２ ５００ミリリットル（ｍＬ）４つ口フラスコにメチルエ
チルケトン３６１.３０ｇを投入し、次いでトリエチル
アミン３１.３７ｇ（０.３１０モル）を投入した。この
溶液にn-ブチルクロライド２５.００ｇ（０.２７０モ
ル）を混合し撹拌を開始した。ジムロート冷却管を装着
した後、オイルバスにより徐々に加熱した。昇温開始２
時間後に液温６９℃で還流が始まった。以後、還流を続
けながら徐々に昇温し、１０時間で７９℃に達し、これ
以上の温度上昇はなくなった。この間、溶液の状態とし
ては、昇温開始直後からスラリー化し始め、徐々にスラ
リー濃度が濃くなった。昇温開始から全１２時間後に反
応液を薄層クロマトグラフィーにより分析した結果、 n
-ブチルクロライドの消失を確認し反応を終了した。こ
のスラリーを２５℃まで冷却し、濾過分離した結晶を少
量のメチルエチルケトンで洗浄した後、５０ｍｍＨｇの
減圧下、６０℃で乾燥した結果、白色粉末であるn-ブチ
ルトリエチルアンモニウムクロライド５０.５９ｇを収
率９６.７％で得た。元素重量分析の結果、Ｃ６１.９
１、Ｈ１２.５１、Ｎ７.２２、Cl１８.３４％（ 理論重
量Ｃ６１.９９、Ｈ１２.４９、Ｎ７.２３、Cl１８.３０
％）であった。Example 2 A 500 ml (mL) four-necked flask was charged with 361.30 g of methyl ethyl ketone, and then charged with 31.37 g (0.310 mol) of triethylamine. 25.00 g (0.270 mol) of n-butyl chloride was mixed with this solution, and stirring was started. After the Dimroth cooling tube was attached, it was gradually heated by an oil bath. Heating start 2
After an hour, reflux started at a liquid temperature of 69 ° C. Thereafter, the temperature was gradually increased while continuing the reflux, and reached 79 ° C. in 10 hours, and no further temperature increase was observed. During this time, the state of the solution began to be slurry immediately after the start of the temperature rise, and the slurry concentration gradually increased. As a result of analyzing the reaction solution by thin-layer chromatography 12 hours after the start of the temperature rise, n
The reaction was terminated after confirming the disappearance of -butyl chloride. The slurry was cooled to 25 ° C., and the crystals separated by filtration were washed with a small amount of methyl ethyl ketone, and dried at 60 ° C. under a reduced pressure of 50 mmHg. As a result, 50.59 g of n-butyltriethylammonium chloride as a white powder was obtained. Obtained at 96.7%. As a result of elemental weight analysis, C61.9 was obtained.
1, H12.51, N7.22, Cl 18.34% (theoretical weight C61.99, H12.49, N7.23, Cl18.30
%)Met.
【００１９】実施例３ １リットル（Ｌ）４つ口フラスコにメチルイソブチルケ
トン３８１.１ｇを投入し、ガス分配フィルターを通じ
トリメチルアミンガス４４.３３ｇ（０.７５モル）を吹
き込み溶解した。この溶液にベンジルクロライド７５.
９５g（０.６０モル）を混合し撹拌を開始した。−５℃
に冷却したブラインを通したジムロート冷却管を装着し
た後、オイルバスにより徐々に加熱した。昇温の際に
は、トリメチルアミンが系外に排出されないよう注意深
く加熱し、昇温開始１時間後に液温７１℃で還流が始ま
った。以後、還流を続けながら徐々に昇温し、４時間で
１０５℃に達し、これ以上の温度上昇はなくなった。こ
の間、溶液の状態としては、昇温開始直後からスラリー
化し始め、徐々にスラリー濃度が濃くなった。昇温開始
から全５時間後に反応液を薄層クロマトグラフィーによ
り分析した結果、 クロロベンゼンの消失を確認し反応
を終了した。このスラリーを２５℃まで冷却し、濾過分
離した結晶を少量のメチルイソブチルケトンで洗浄した
後、４０ｍｍＨｇの減圧下、６０℃で乾燥した結果、白
色粉末であるベンジルトリメチルアンモニウムクロライ
ド１０９.６４ｇを収率９８.４％で得た。元素重量分析
の結果、Ｃ６4.７０、Ｈ８.６２、Ｎ７.５３、Cl１９.
１６％（ 理論重量Ｃ６４.６８、Ｈ８.６８、Ｎ７.５
４、 Cl１９.０９％）であった。Example 3 381.1 g of methyl isobutyl ketone was charged into a 1 liter (L) four-necked flask, and 44.33 g (0.75 mol) of trimethylamine gas was blown through a gas distribution filter to dissolve. Benzyl chloride 75.
95 g (0.60 mol) were mixed and stirring was started. -5 ° C
After installing a Dimroth condenser through which cooled brine was passed, the mixture was gradually heated by an oil bath. At the time of temperature rise, heating was performed carefully so that trimethylamine was not discharged out of the system. One hour after the start of the temperature rise, reflux started at a liquid temperature of 71 ° C. Thereafter, the temperature was gradually increased while the reflux was continued, and reached 105 ° C. in 4 hours. During this time, the state of the solution began to be slurry immediately after the start of the temperature rise, and the slurry concentration gradually increased. After a total of 5 hours from the start of the temperature rise, the reaction solution was analyzed by thin-layer chromatography. As a result, the disappearance of chlorobenzene was confirmed, and the reaction was terminated. The slurry was cooled to 25 ° C., and the crystals separated by filtration were washed with a small amount of methyl isobutyl ketone, and dried at 60 ° C. under a reduced pressure of 40 mmHg. As a result, 109.64 g of benzyltrimethylammonium chloride as a white powder was obtained. Obtained at 98.4%. As a result of elemental weight analysis, C64.70, H8.62, N7.53, Cl19.
16% (theoretical weight C64.68, H8.68, N7.5
4, Cl 19.09%).
【００２０】比較例１ ５００ミリリットル（ｍＬ）４つ口フラスコにエタノー
ル２８０.５６ｇを投入し、ガス分配フィルターを通じ
トリメチルアミンガス１７.３０ｇ（０.２９３モル）を
吹き込み溶解した。この溶液にn-ドデシルブロマイド５
６.１１ｇ（０.２２５モル）を混合し撹拌を開始した。
−５℃に冷却したブラインを通したジムロート冷却管を
装着した後、オイルバスにより徐々に加熱した。昇温の
際には、トリメチルアミンが系外に排出されないよう注
意深く加熱し、昇温開始２時間後に液温７６℃で還流が
始まった。以後、還流を続けながら１時間反応を行っ
た。この間、溶液の状態としては、無色透明の状態が続
いた。昇温開始から全３時間後に反応液を薄層クロマト
グラフィーにより分析した結果、 n-ドデシルブロマイ
ドの消失を確認し反応を終了した。このスラリーを５℃
まで冷却しても結晶がほとんど析出しないため、エタノ
ールを１４１.７ｇ減圧留去し、続いて５℃まで冷却し
た後濾過分離を行った。得られた結晶は濾過途中で吸湿
し潮解性を帯びてきたので、リンス洗浄することなく素
早く乾燥を行った。４０ｍｍＨｇの減圧下、６０℃で乾
燥した結果、白色粉末であるn-ドデシルトリメチルアン
モニウムブロマイド３７.２４ｇを収率５３.６％で得
た。元素重量分析の結果、Ｃ５８.３６、Ｈ１１.１０、
Ｎ４.５２、Br２５.９６％であった。また、濾過母液を
濃縮乾固し、淡黄白色固体３１.１１ｇを得た。元素重
量分析の結果、Ｃ５８.４３、Ｈ１１.０４、Ｎ４.３
８、Br２６.１６％であった。共に理論重量はＣ５８.４
３、Ｈ１１.１１、Ｎ４.５３、Br２５.９３％である。Comparative Example 1 Ethanol (280.56 g) was charged into a 500 ml (mL) four-necked flask, and 17.30 g (0.293 mol) of trimethylamine gas was blown through a gas distribution filter to dissolve. Add n-dodecyl bromide 5 to this solution.
6.11 g (0.225 mol) were mixed and stirring was started.
After installing a Dimroth condenser through which the brine was cooled to -5 ° C, the mixture was gradually heated by an oil bath. At the time of heating, heating was performed carefully so that trimethylamine was not discharged out of the system, and reflux started at a liquid temperature of 76 ° C. 2 hours after the start of heating. Thereafter, the reaction was carried out for 1 hour while continuing the reflux. During this time, the solution remained colorless and transparent. The reaction solution was analyzed by thin-layer chromatography three hours after the start of the temperature rise. As a result, disappearance of n-dodecyl bromide was confirmed, and the reaction was terminated. This slurry is 5 ℃
Since almost no crystals were precipitated even when cooled, 141.7 g of ethanol was distilled off under reduced pressure, followed by cooling to 5 ° C. and filtration separation. The obtained crystals absorbed moisture during the filtration and became deliquescent. Therefore, the crystals were quickly dried without rinsing. As a result of drying at 60 ° C. under a reduced pressure of 40 mmHg, 37.24 g of n-dodecyltrimethylammonium bromide as a white powder was obtained at a yield of 53.6%. As a result of elemental weight analysis, C58.36, H11.10,
N 4.52 and Br 25.96%. Further, the filtrated mother liquor was concentrated to dryness to obtain 31.11 g of a pale yellow-white solid. As a result of elemental weight analysis, C58.43, H11.04, N4.3.
8, Br 26.16%. Both have a theoretical weight of C58.4
3, H11.11, N4.53, Br25.93%.
【００２１】[0021]
【発明の効果】本発明の製造方法に従って、テトラアル
キルアンモニウムハライドをほとんど溶解することのな
い非プロトン性溶媒中で、原料であるハロゲン化炭化水
素と３級アミンを反応させ、溶媒に溶解することなく析
出してきたテトラアルキルアンモニウムハライドの結晶
を室温状態で濾過分離し、洗浄後、減圧乾燥することに
より、高収率で高純度のテトラアルキルアンモニウムハ
ライドを製造することができる。According to the production method of the present invention, a halogenated hydrocarbon as a raw material is reacted with a tertiary amine in an aprotic solvent that hardly dissolves a tetraalkylammonium halide and dissolved in a solvent. Crystals of tetraalkylammonium halide precipitated without filtration are separated by filtration at room temperature, washed, and dried under reduced pressure, whereby a high-purity tetraalkylammonium halide can be produced in high yield.
Claims (5)
素又は、炭素数３〜２４の脂環族または芳香族を含む炭
化水素基）で表されるハロゲン化炭化水素と、一般式
（２） 【化２】 （ Ｒ２、 Ｒ３、 Ｒ４は炭素数１〜２４の脂肪族炭化
水素又は、炭素数３〜２４の脂環族または芳香族を含む
炭化水素基）で表される３級アミンを、非プロトン性溶
媒中で反応させることを特徴とする一般式（３） 【化３】 （ Ｒ１、 Ｒ２、 Ｒ３、 Ｒ４及びXは前記と同様）で
表されるテトラアルキルアンモニウムハライドの製造方
法。1. A compound of the general formula (1) (X is a halogen, R1 is an aliphatic hydrocarbon having 1 to 24 carbon atoms or an alicyclic or aromatic hydrocarbon group having 3 to 24 carbon atoms) and a halogenated hydrocarbon represented by the general formula ( 2) (R2, R3, R4 is an aliphatic hydrocarbon having 1 to 24 carbon atoms or an alicyclic or aromatic hydrocarbon group having 3 to 24 carbon atoms) represented by an aprotic solvent General formula (3) characterized in that the reaction is carried out in (Wherein R1, R2, R3, R4 and X are the same as described above).
式（３） 【化４】 で表されるテトラアルキルアンモニウムハライドをほと
んど溶解しないエステル類、ケトン類、エーテル類であ
る請求項１の方法。2. The aprotic solvent according to claim 1, wherein the aprotic solvent is represented by the general formula (3). 2. The method according to claim 1, wherein the compound is an ester, ketone or ether which hardly dissolves the tetraalkylammonium halide represented by the formula:
を室温〜反応終了物の沸点温度の範囲内で非プロトン溶
媒と分離することを特徴とする一般式（３） 【化５】 で表されるテトラアルキルアンモニウムハライドの製造
方法。3. The general formula (3) according to claim 1, wherein after the completion of the reaction, the precipitate is separated from the aprotic solvent within the range from room temperature to the boiling point of the reaction product. A method for producing a tetraalkylammonium halide represented by the formula:
が炭素数１〜18の脂肪族炭化水素または、炭素数３〜12
の脂環族または芳香族を含む炭化水素基であり、Ｒ２、
Ｒ３、 Ｒ４が炭素数１〜18の脂肪族炭化水素または、
炭素数３〜12の脂環族または芳香族を含む炭化水素基で
あり、Ｘが塩素または臭素であり、溶媒が酢酸エチル、
酢酸ブチル、メチルエチルケトン、メチルイソブチルケ
トン、テトラヒドロフラン、１.４−ジオキサンである
請求項１〜３の方法。4. A compound of the general formula (3) R1 of a tetraalkylammonium halide represented by
Is an aliphatic hydrocarbon having 1 to 18 carbon atoms or 3 to 12 carbon atoms
An alicyclic or aromatic-containing hydrocarbon group of R2,
R3, R4 is an aliphatic hydrocarbon having 1 to 18 carbon atoms, or
An alicyclic or aromatic hydrocarbon group having 3 to 12 carbon atoms, X is chlorine or bromine, the solvent is ethyl acetate,
4. The method according to claim 1, which is butyl acetate, methyl ethyl ketone, methyl isobutyl ketone, tetrahydrofuran, 1.4-dioxane.
デシルトリメチルアンモニウムブロマイドであり、溶媒
が酢酸ブチルである請求項１〜４の方法。5. A compound of the general formula (3) The method according to claim 1, wherein the tetraalkylammonium halide represented by the formula is n-dodecyltrimethylammonium bromide, and the solvent is butyl acetate.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003095414A1 (en) * | 2002-05-14 | 2003-11-20 | Stella Chemifa Kabushiki Kaisha | Method of purifying quaternary alkylammonium salt and quaternary alkylammonium salt |
| CN106916068A (en) * | 2017-03-24 | 2017-07-04 | 吴琏 | A kind of simple and convenient benzalkonium chloride production method |
| CN106916071A (en) * | 2017-03-24 | 2017-07-04 | 吴琏 | The synthetic method of benzalkonium chloride mixture |
| CN106946716A (en) * | 2017-03-24 | 2017-07-14 | 吴琏 | A kind of benzalkonium chloride monomer synthesis technique |
| CN109232269A (en) * | 2018-10-31 | 2019-01-18 | 江西肯特化学有限公司 | A kind of method of one step Bei Benzyl base front three ammonium chloride of semidry process |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000026473A (en) * | 1998-07-07 | 2000-01-25 | Sumitomo Seika Chem Co Ltd | Production of quaternary alkylammonium tetrafluoroborate |
| JP2000229917A (en) * | 1999-02-12 | 2000-08-22 | Mitsubishi Rayon Co Ltd | Method for producing unsaturated quaternary ammonium salt |
-
2000
- 2000-07-12 JP JP2000210627A patent/JP2002030044A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000026473A (en) * | 1998-07-07 | 2000-01-25 | Sumitomo Seika Chem Co Ltd | Production of quaternary alkylammonium tetrafluoroborate |
| JP2000229917A (en) * | 1999-02-12 | 2000-08-22 | Mitsubishi Rayon Co Ltd | Method for producing unsaturated quaternary ammonium salt |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003095414A1 (en) * | 2002-05-14 | 2003-11-20 | Stella Chemifa Kabushiki Kaisha | Method of purifying quaternary alkylammonium salt and quaternary alkylammonium salt |
| CN1298698C (en) * | 2002-05-14 | 2007-02-07 | 斯特拉化学株式会社 | Method of purifying quaternary alkylammonium salt and quaternary alkylammonium salt |
| US7268256B2 (en) | 2002-05-14 | 2007-09-11 | Stella Chemifa Kabushiki Kaisha | Method of purifying quaternary alkyl ammonium salt and quaternary alkyl ammonium salt |
| KR100994089B1 (en) | 2002-05-14 | 2010-11-12 | 스텔라 케미파 코포레이션 | Purification method of quaternary alkylammonium salts and quaternary alkylammonium salts |
| CN106916068A (en) * | 2017-03-24 | 2017-07-04 | 吴琏 | A kind of simple and convenient benzalkonium chloride production method |
| CN106916071A (en) * | 2017-03-24 | 2017-07-04 | 吴琏 | The synthetic method of benzalkonium chloride mixture |
| CN106946716A (en) * | 2017-03-24 | 2017-07-14 | 吴琏 | A kind of benzalkonium chloride monomer synthesis technique |
| CN106946716B (en) * | 2017-03-24 | 2019-03-01 | 广东洛斯特制药有限公司 | Process for synthesizing benzalkonium chloride monomer |
| CN106916068B (en) * | 2017-03-24 | 2019-03-01 | 广东洛斯特制药有限公司 | Simple and convenient benzalkonium chloride production method |
| CN109232269A (en) * | 2018-10-31 | 2019-01-18 | 江西肯特化学有限公司 | A kind of method of one step Bei Benzyl base front three ammonium chloride of semidry process |
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