JPS6250459B2 - - Google Patents
Info
- Publication number
- JPS6250459B2 JPS6250459B2 JP7373980A JP7373980A JPS6250459B2 JP S6250459 B2 JPS6250459 B2 JP S6250459B2 JP 7373980 A JP7373980 A JP 7373980A JP 7373980 A JP7373980 A JP 7373980A JP S6250459 B2 JPS6250459 B2 JP S6250459B2
- Authority
- JP
- Japan
- Prior art keywords
- reaction
- nitroparaffins
- alkali metal
- chloride
- phase
- 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.)
- Expired
Links
- 238000006243 chemical reaction Methods 0.000 claims description 26
- -1 alkali metal nitrite salt Chemical class 0.000 claims description 23
- 229910052783 alkali metal Inorganic materials 0.000 claims description 20
- 150000001348 alkyl chlorides Chemical class 0.000 claims description 14
- 239000012074 organic phase Substances 0.000 claims description 12
- 239000008346 aqueous phase Substances 0.000 claims description 11
- 239000003444 phase transfer catalyst Substances 0.000 claims description 11
- 238000004519 manufacturing process Methods 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 9
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 238000000034 method Methods 0.000 description 34
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 20
- 239000002994 raw material Substances 0.000 description 14
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 12
- 235000010288 sodium nitrite Nutrition 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 description 8
- 150000001350 alkyl halides Chemical class 0.000 description 7
- GZUXJHMPEANEGY-UHFFFAOYSA-N bromomethane Chemical compound BrC GZUXJHMPEANEGY-UHFFFAOYSA-N 0.000 description 6
- 229940050176 methyl chloride Drugs 0.000 description 6
- 239000012071 phase Substances 0.000 description 5
- MCSAJNNLRCFZED-UHFFFAOYSA-N nitroethane Chemical compound CC[N+]([O-])=O MCSAJNNLRCFZED-UHFFFAOYSA-N 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 125000001931 aliphatic group Chemical group 0.000 description 3
- 150000001347 alkyl bromides Chemical class 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 229940102396 methyl bromide Drugs 0.000 description 3
- 239000002798 polar solvent Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- ZFFMLCVRJBZUDZ-UHFFFAOYSA-N 2,3-dimethylbutane Chemical compound CC(C)C(C)C ZFFMLCVRJBZUDZ-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- AZFNGPAYDKGCRB-XCPIVNJJSA-M [(1s,2s)-2-amino-1,2-diphenylethyl]-(4-methylphenyl)sulfonylazanide;chlororuthenium(1+);1-methyl-4-propan-2-ylbenzene Chemical compound [Ru+]Cl.CC(C)C1=CC=C(C)C=C1.C1=CC(C)=CC=C1S(=O)(=O)[N-][C@@H](C=1C=CC=CC=1)[C@@H](N)C1=CC=CC=C1 AZFNGPAYDKGCRB-XCPIVNJJSA-M 0.000 description 2
- 150000001351 alkyl iodides Chemical class 0.000 description 2
- 150000001450 anions Chemical group 0.000 description 2
- HTZCNXWZYVXIMZ-UHFFFAOYSA-M benzyl(triethyl)azanium;chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC1=CC=CC=C1 HTZCNXWZYVXIMZ-UHFFFAOYSA-M 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 150000001805 chlorine compounds Chemical class 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- SHFJWMWCIHQNCP-UHFFFAOYSA-M hydron;tetrabutylazanium;sulfate Chemical compound OS([O-])(=O)=O.CCCC[N+](CCCC)(CCCC)CCCC SHFJWMWCIHQNCP-UHFFFAOYSA-M 0.000 description 2
- 239000005457 ice water Substances 0.000 description 2
- BLLFVUPNHCTMSV-UHFFFAOYSA-N methyl nitrite Chemical compound CON=O BLLFVUPNHCTMSV-UHFFFAOYSA-N 0.000 description 2
- XKBGEWXEAPTVCK-UHFFFAOYSA-M methyltrioctylammonium chloride Chemical compound [Cl-].CCCCCCCC[N+](C)(CCCCCCCC)CCCCCCCC XKBGEWXEAPTVCK-UHFFFAOYSA-M 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 2
- 235000010289 potassium nitrite Nutrition 0.000 description 2
- 239000004304 potassium nitrite Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- VMKOFRJSULQZRM-UHFFFAOYSA-N 1-bromooctane Chemical compound CCCCCCCCBr VMKOFRJSULQZRM-UHFFFAOYSA-N 0.000 description 1
- GKQHIYSTBXDYNQ-UHFFFAOYSA-M 1-dodecylpyridin-1-ium;chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+]1=CC=CC=C1 GKQHIYSTBXDYNQ-UHFFFAOYSA-M 0.000 description 1
- HDNYJVKFAJFFQX-UHFFFAOYSA-M 1-ethylquinolin-1-ium;chloride Chemical compound [Cl-].C1=CC=C2[N+](CC)=CC=CC2=C1 HDNYJVKFAJFFQX-UHFFFAOYSA-M 0.000 description 1
- KLGHUFNKRIWCDQ-UHFFFAOYSA-N 1-nitrooctane Chemical compound CCCCCCCC[N+]([O-])=O KLGHUFNKRIWCDQ-UHFFFAOYSA-N 0.000 description 1
- JSZOAYXJRCEYSX-UHFFFAOYSA-N 1-nitropropane Chemical compound CCC[N+]([O-])=O JSZOAYXJRCEYSX-UHFFFAOYSA-N 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
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- VUEDNLCYHKSELL-UHFFFAOYSA-N arsonium Chemical group [AsH4+] VUEDNLCYHKSELL-UHFFFAOYSA-N 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- NEHMKBQYUWJMIP-NJFSPNSNSA-N chloro(114C)methane Chemical compound [14CH3]Cl NEHMKBQYUWJMIP-NJFSPNSNSA-N 0.000 description 1
- HRYZWHHZPQKTII-UHFFFAOYSA-N chloroethane Chemical compound CCCl HRYZWHHZPQKTII-UHFFFAOYSA-N 0.000 description 1
- 230000009918 complex formation Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 150000003983 crown ethers Chemical class 0.000 description 1
- 239000002739 cryptand Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- BBGKDYHZQOSNMU-UHFFFAOYSA-N dicyclohexano-18-crown-6 Chemical compound O1CCOCCOC2CCCCC2OCCOCCOC2CCCCC21 BBGKDYHZQOSNMU-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229960003750 ethyl chloride Drugs 0.000 description 1
- 238000005755 formation reaction Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 150000004694 iodide salts Chemical class 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- SNMVRZFUUCLYTO-UHFFFAOYSA-N n-propyl chloride Chemical compound CCCCl SNMVRZFUUCLYTO-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 150000002826 nitrites Chemical class 0.000 description 1
- 150000002828 nitro derivatives Chemical class 0.000 description 1
- 238000006053 organic reaction Methods 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 150000004714 phosphonium salts Chemical group 0.000 description 1
- 125000003367 polycyclic group Chemical group 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 150000003222 pyridines Chemical class 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 150000003839 salts Chemical group 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- DZLFLBLQUQXARW-UHFFFAOYSA-N tetrabutylammonium Chemical compound CCCC[N+](CCCC)(CCCC)CCCC DZLFLBLQUQXARW-UHFFFAOYSA-N 0.000 description 1
- IUVXCVGGLRYGFE-UHFFFAOYSA-N tetraphenyl-lambda5-arsane hydrochloride Chemical compound C1=CC=C(C=C1)[AsH](C2=CC=CC=C2)(C3=CC=CC=C3)C4=CC=CC=C4.Cl IUVXCVGGLRYGFE-UHFFFAOYSA-N 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- GNMJFQWRASXXMS-UHFFFAOYSA-M trimethyl(phenyl)azanium;bromide Chemical compound [Br-].C[N+](C)(C)C1=CC=CC=C1 GNMJFQWRASXXMS-UHFFFAOYSA-M 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
本発明は、炭素原子数１〜３の低級塩化アルキ
ルと亜硝酸アルカリ金属塩をそれぞれ異る二つの
液相に存在させ、二液相間に相間移動触媒を使用
して反応させることにより対応する低級ニトロパ
ラフイン類、すなわちニトロメタン、ニトロエタ
ンまたはニトロプロパンを選択的に製造する方法
に関する。
低級ニトロパラフイン類の工業的製造法として
は、過剰のプロパンを硝酸とともに加圧下、高温
に加熱し、より短鎖の化合物への分解を伴うニト
ロ化によつて、低級ニトロパラフイン類の混合生
成物を得、ついでこの混合物から目的とするニト
ロパラフインを分離する方法が実施されている。
しかし、この方法は反応の選択性がなく、数種の
ニトロパラフインを同時に生成するので、目的の
ニトロパラフインを分離することが煩雑な上、併
産されるニトロパラフインが総合的に利用されな
ければ、経済的に有利な方法とは言えない。
選択的にニトロパラフイン類を得る方法とし
て、高級ニトロパラフインの合成に関しては、高
級ハロゲン化アルキルと亜硝酸アルカリ金属をジ
メチルスルホキシドやジメチルホルムアミドなど
の非プロトン性極性溶媒中で反応させることによ
り、合成する方法が知られている。（Roger
Adams他監集“Organic Reactions”第12巻、第
３章、John Wiley and Sons，Inc.，1962年）。
しかし、この方法では使用される原料の高級ハロ
ゲン化アルキルは臭化物または沃化物に限られる
ので、原料が極めて高価である。安価な塩化物で
はほとんど反応しないことが明らかにされてい
る。
低級のハロゲン化アルキルと亜硝酸アルカリ金
属塩との反応による低級ニトロパラフインの製造
法に関しては、ニトロメタンの製造法として塩化
メチルまたは臭化メチルと亜硝酸アルカリ金属塩
とを水溶媒中で加熱反応させる方法が知られてい
る（米国特許第2105581号、および同第2117931
号）。しかしながら、この方法で塩化メチルを原
料とする場合には、極めて低収率であり、選択性
も低く工業化されるには程遠い。これは亜硝酸ア
ルカリ金属塩を水溶液中で加熱するため、その熱
変質がさけ難いためである。また、臭化メチルを
原料とする場合には、より高い収率を与えるが、
原料としての臭化メチルが高価なため工業的には
実施されていない。
したがつて、低級ハロゲン化アルキルと亜硝酸
アルカリ金属塩との反応による低級ニトロパラフ
インの製造法としては、安価な塩化物が原料とし
て使えること、かつ反応条件が温和で反応物およ
び生成物の変質がなく選択性よく生成物が得られ
なければ実用化できない。また、この反応では、
ニトロ化合物と同時に亜硝酸アルキルエステルを
副生するので、その副生をいかに抑制するかが重
要な問題となる。
本発明者らは、先に、低級塩化アルキルと亜硝
酸アルカリ金属塩とを非プロトン性極性溶媒中で
反応させることにより、高収率で低級ニトロパラ
フインが製造できることを見出し、その方法を開
示した（特開昭54−125604）。この方法は極めて
簡便な方法であるうえ、反応条件も温和であり、
収率も高い、しかし、使用する非プロトン性極性
溶媒が比較的高価なことが難点である。
本発明者らは、これらの問題を解決するため、
安価な汎用の単一溶媒、混合溶媒または二種の相
混わらない溶媒中での塩化メチルと亜硝酸アルカ
リ金属塩との反応性や反応条件等を鋭意検討した
結果、亜硝酸アルカリ金属塩を水溶液とし、塩化
メチルを無溶媒のままかまたは汎用の水と混り合
わない有機溶媒に溶解し、その水相と有機相との
間に相間移動触媒を使用して、温和な条件で反応
させることにより、驚べきことに極めて高い選択
率でニトロメタンが製造できることを見出し、本
発明を完成した。
相間移動触媒を使用してニトロパラフインを製
造する方法としては、既に高級のハロゲン化アル
キルと亜硝酸アルカリ金属塩との反応で、高級の
ニトロパラフインを得る方法が公知であるが、こ
の方法では、原料のハロゲン化アルキルは、高級
アルキルの、しかも臭化物または沃化物に限ら
れ、塩化物を使用する例はない。さらに、水―有
機相間の相間移動法によるｎ―オクチルブロマイ
ドと亜硝酸ナトリウムとの反応では、高々19％の
ニトロオクタンが生成するに過ぎず、その選択率
に関する記載はない（旭硝子工業技術奨励会報告
24巻、59頁、1974年）。また、固―有機相間の相
間移動法によれば、高級ニトロパラフインが高級
臭化アルキルまたは高級沃化アルキルから50〜70
％の収率で得られてはいる（Tetrahedron
Letters1号，71頁，1975年）。つまり、これらの
方法は高級ニトロパラフインを得ることを目的と
したもの、しかも、原料として高価な臭化アルキ
ルまたは沃化アルキルを使用して反応させるもの
であり、低級塩化アルキルを使用して低級ニトロ
パラフインを得る本発明の反応とは根本的にその
反応性が異なる。すなわち、低級塩化アルキルと
亜硝酸アルカリ金属塩から相間移動法で低級ニト
ロパラフインを製造する方法は未だ知られておら
ず、新規な方法である。
すなわち、本発明の方法は、低級塩化アルキル
を無溶媒のまま、または水と混り合わない有機溶
媒に溶解して有機相とし、亜硝酸アルカリ金属塩
は水に溶解して水相とし、水相からニトロ基を有
機相に移動させる相間移動触媒を使用して両原料
を反応させ、対応する低級ニトロパラフインを選
択的に製造する方法である。
したがつて、本発明の方法は、原料として、ハ
ロゲン化アルキル中最も安価で容易に入手可能な
低級塩化アルキルを使用し、必要に応じて使用す
る溶媒としては安価で汎用のものが使用できるこ
と、相間移動触媒を用いて温和な条件下に、選択
性よく低級ニトロパラフインが得られるところに
特徴がある。
本発明の方法に用いる低級塩化アルキルとは、
炭素原子数１〜３の塩化アルキルであつて、塩化
メチル、塩化エチルおよび塩化プロピルである。
本発明の方法に用いる原料の低級塩化アルキル
は無溶媒のまま使用してもまたは水と混り合わな
い有機溶媒に溶解して使用してもよい。この濃度
は、特に制限はないが稀薄すぎては反応が遅くな
るので、通常１〜100重量％の範囲である。
必要に応じて使用する溶媒としては、水との相
溶性の低いものが好ましく、例えば石油エーテ
ル、ｎ―ヘキサン、２，３ジメチルブタンのよう
な直鎖または分岐の脂肪族炭化水素類、例えば、
シクロヘキサンのような脂肪族環状炭化水素類、
例えばベンゼン、トルエンのような無置換または
脂肪族炭化水素基の置換した芳香族炭化水素類な
どであるが、反応条件下に安定であり、反応物、
生成物および触媒に対して、反応したりまたは二
液相系の成立に悪影響を与えたりしない限り、い
かなる置換基、結合、官能基を有する溶媒でも使
用できる。
本発明の方法に用いる亜硝酸アルカリ金属塩
は、亜硝酸ナトリウムまたは亜硝酸カリウムであ
る。これらの亜硝酸塩は水に溶解させて使用する
が、その濃度に特に制限はない。また飽和濃度以
上で固体が共存していてもよい。通常は１重量％
〜飽和濃度程度であり、濃度が低すぎると反応速
度が遅くなり好ましくない。
本発明の方法において、塩化アルキルと亜硝酸
アルカリ金属塩の使用量は両者が等モル反応の原
料であり、したがつてその本質的には特に限定さ
れるものではないが、塩化アルキル１モルに対し
て亜硝酸塩を、通常、0.01〜100モル、好ましく
は0.1〜10モルの割合で用いられる。なお過剰に
用いられた原料は、反応後に未反応物として残存
するが、慣用の蒸留、分液などの分離操作で容易
に分離回収し再使用することができる。
本発明の方法に用いる相間移動触媒としては、
つぎのようなものである。すなわち、(a)一般式
R1・R2・R3・R4・Ｎ・Ｘ（ここでR1，R2，R3，
R4は同種もしくは異種の脂肪族炭化水素基また
は芳香族炭化水素基、あるいは芳香族の置換した
脂肪族炭化水素基、またはこれらの組合せであ
り、Ｘはハロゲンアニオンまたは他種のアニオ
ン）で示される四級アンモニウム塩、例えば、ベ
ンジルトリエチルアンモニウムクロライド、フエ
ニルトリメチルアンモニウムブロマイド、トリオ
クチルメチルアンモニウムクロライド、テトラブ
チルアンモニウム硫酸水素塩などがある。(b)、一
般式
In the present invention, a lower alkyl chloride having 1 to 3 carbon atoms and an alkali metal nitrite salt are present in two different liquid phases, and a phase transfer catalyst is used between the two liquid phases to react with each other. The present invention relates to a method for selectively producing lower nitroparaffins, namely nitromethane, nitroethane or nitropropane. An industrial method for producing lower nitroparaffins is to heat excess propane together with nitric acid under pressure and high temperature, and nitrate with decomposition into shorter chain compounds to produce a mixed product of lower nitroparaffins. A method has been implemented in which the desired nitroparaffin is obtained and then the target nitroparaffin is separated from this mixture.
However, this method lacks reaction selectivity and produces several types of nitroparaffins at the same time, making it complicated to separate the desired nitroparaffins, and the co-produced nitroparaffins must be utilized comprehensively. , cannot be said to be an economically advantageous method. As a method for selectively obtaining nitroparaffins, higher nitroparaffins are synthesized by reacting higher alkyl halides and alkali metal nitrites in an aprotic polar solvent such as dimethyl sulfoxide or dimethylformamide. method is known. (Roger
Adams et al., "Organic Reactions," Volume 12, Chapter 3, John Wiley and Sons, Inc., 1962).
However, in this method, the raw material higher alkyl halide used is limited to bromide or iodide, so the raw material is extremely expensive. It has been shown that cheap chloride hardly reacts. Regarding the method for producing lower nitroparaffins by the reaction of lower alkyl halides and alkali metal nitrites, the method for producing nitromethane involves heating reaction of methyl chloride or methyl bromide with alkali metal nitrites in an aqueous solvent. Methods are known (U.S. Pat. Nos. 2,105,581 and 2,117,931).
issue). However, when this method uses methyl chloride as a raw material, the yield is extremely low, the selectivity is low, and it is far from being industrialized. This is because the alkali metal nitrite salt is heated in an aqueous solution, so it is difficult to avoid thermal deterioration. In addition, when using methyl bromide as a raw material, higher yields are obtained, but
This method has not been implemented industrially because methyl bromide as a raw material is expensive. Therefore, as a method for producing lower nitroparaffins by reacting lower alkyl halides with alkali metal nitrites, inexpensive chlorides can be used as raw materials, the reaction conditions are mild, and the alteration of reactants and products is avoided. It cannot be put to practical use unless a product is obtained with good selectivity. Also, in this reaction,
Since nitrite alkyl ester is produced as a by-product at the same time as the nitro compound, an important issue is how to suppress this by-product. The present inventors have previously discovered that lower nitroparaffins can be produced in high yield by reacting lower alkyl chlorides and alkali metal nitrites in an aprotic polar solvent, and have disclosed the method. (Japanese Patent Application Laid-Open No. 54-125604). This method is extremely simple, and the reaction conditions are mild.
The yield is also high, but the disadvantage is that the aprotic polar solvent used is relatively expensive. In order to solve these problems, the present inventors
As a result of intensive studies on the reactivity and reaction conditions of methyl chloride and alkali metal nitrite in an inexpensive general-purpose single solvent, a mixed solvent, or two types of immiscible solvents, we found that alkali metal nitrite was Make an aqueous solution, methyl chloride is dissolved in a general-purpose organic solvent that is immiscible with water, and the reaction is carried out under mild conditions using a phase transfer catalyst between the aqueous phase and the organic phase. As a result, they surprisingly discovered that nitromethane could be produced with extremely high selectivity, and completed the present invention. As a method for producing nitroparaffins using a phase transfer catalyst, a method is already known in which high-grade nitroparaffins are obtained by reacting a high-grade alkyl halide with an alkali metal nitrite; however, in this method, The alkyl halides used as raw materials are limited to higher alkyl bromides or iodides, and there are no examples of using chlorides. Furthermore, in the reaction of n-octyl bromide and sodium nitrite using a phase transfer method between water and organic phases, only 19% of nitrooctane is produced, and there is no mention of its selectivity (Asahi Glass Industrial Technology Promotion Association). report
Volume 24, page 59, 1974). Furthermore, according to the phase transfer method between solid and organic phases, higher nitroparaffins can be converted from higher alkyl bromides or higher alkyl iodides by 50 to 70%.
% yield (Tetrahedron
Letters No. 1, p. 71, 1975). In other words, these methods are aimed at obtaining higher nitroparaffins, and they involve reactions using expensive alkyl bromides or alkyl iodides as raw materials, whereas lower alkyl chlorides are used to produce lower nitroparaffins. The reactivity is fundamentally different from the reaction of the present invention to obtain paraffin. That is, a method for producing lower nitroparaffins from lower alkyl chloride and alkali metal nitrite by a phase transfer method is not yet known, and is a new method. That is, in the method of the present invention, the lower alkyl chloride is dissolved without a solvent or in an organic solvent that is immiscible with water to form an organic phase, and the alkali metal nitrite is dissolved in water to form an aqueous phase. This is a method for selectively producing the corresponding lower nitroparaffins by reacting both raw materials using a phase transfer catalyst that transfers nitro groups from the phase to the organic phase. Therefore, the method of the present invention uses lower alkyl chloride, which is the cheapest and easily available among alkyl halides, as a raw material, and if necessary, an inexpensive and general-purpose solvent can be used. It is characterized by the fact that lower nitroparaffins can be obtained with good selectivity under mild conditions using a phase transfer catalyst. The lower alkyl chloride used in the method of the present invention is
Alkyl chlorides having 1 to 3 carbon atoms, such as methyl chloride, ethyl chloride and propyl chloride. The raw material lower alkyl chloride used in the method of the present invention may be used without a solvent or dissolved in an organic solvent that is immiscible with water. This concentration is not particularly limited, but if it is too dilute, the reaction will be slow, so it is usually in the range of 1 to 100% by weight. The solvent to be used as necessary is preferably one with low compatibility with water, such as petroleum ether, n-hexane, linear or branched aliphatic hydrocarbons such as 2,3 dimethyl butane, etc.
aliphatic cyclic hydrocarbons such as cyclohexane,
For example, aromatic hydrocarbons such as benzene and toluene, which are unsubstituted or substituted with an aliphatic hydrocarbon group, are stable under the reaction conditions, and the reactants,
Any solvent having any substituent, bond, or functional group can be used as long as it does not react with the product or catalyst or adversely affect the establishment of the two-liquid phase system. The alkali metal nitrite salt used in the method of the invention is sodium nitrite or potassium nitrite. These nitrites are used after being dissolved in water, but there are no particular restrictions on their concentration. Further, solids may coexist at a saturation concentration or higher. Usually 1% by weight
- about a saturation concentration; if the concentration is too low, the reaction rate will slow down, which is undesirable. In the method of the present invention, the amounts of alkyl chloride and alkali metal nitrite to be used are not particularly limited since both are raw materials for the reaction in equimolar amounts; On the other hand, nitrite is usually used in a proportion of 0.01 to 100 mol, preferably 0.1 to 10 mol. Note that the raw material used in excess remains as an unreacted material after the reaction, but it can be easily separated and recovered by conventional separation operations such as distillation and liquid separation and reused. The phase transfer catalyst used in the method of the present invention includes:
It is as follows. That is, (a) general formula
R 1・R 2・R 3・R 4・N・X (here R 1 , R 2 , R 3 ,
R 4 is the same or different aliphatic hydrocarbon group or aromatic hydrocarbon group, or an aromatic substituted aliphatic hydrocarbon group, or a combination thereof, and X is a halogen anion or an anion of another type. Examples of quaternary ammonium salts include benzyltriethylammonium chloride, phenyltrimethylammonium bromide, trioctylmethylammonium chloride, and tetrabutylammonium hydrogen sulfate. (b), general formula
【式】（こゝで、R1，R2およ
びＸは上記に同じ）で示される四級ピリジニウム
塩またはピリジン同族体の四級塩、例えば、１―
ドデシルピリジニウムクロライドあるいは１―エ
チルキノリニウムクロライドなどがある。(c)一般
式R1・R2・R3・R4・Ｐ・Ｘ（こゝで、R1，R2，
R3，R4およびＸは上記に同じ）で示される四級
ホスホニウム塩も用いられ、例えばテトラフエニ
ルホスホニウムクロライドあるいはトリオクチル
エチルホスホニウムブロマイドなどがある。(d)一
般式R1・R2・R3・R4・As・Ｘ（こゝで、R1，
R2，R3，R4およびＸは上記に同じ）で示される
四級アルソニウム塩、例えば、テトラフエニルア
ルソニウムクロライドのようなものである。更に
は、(e)大環状ポリエーテル類、いわゆるクラウン
エーテル類、例えばジシクロヘキシル―18―クラ
ウン―６などや、更には多環大環状ポリアミノエ
ーテル、いわゆるクリプタンド類も用いることが
できる。
これらの相間移動触媒は、水相においてイオン
交換反応の過程を経て、亜硝酸アルカリ金属塩の
アニオン部分、すなわちニトロ基のみを水相から
塩化アルキルの存在する有機相へ移動させるか、
あるいは水相において錯体生成反応の過程を経て
亜硝酸アルカリ金属塩を錯体として水相から有機
相へ移す働きをする。
本発明の方法に使用するこれらの相間移動触媒
の使用量は、特に制限がないがわ、通常、使用す
る亜硝酸アルカリ金属塩の１モルに対して0.001
〜１モルである。
本発明の方法における反応温度は５〜90℃であ
り、好ましくは15〜40℃、通常、常温である。反
応圧力は、通常、常圧ないし５Kg／cm2Ｇの間であ
るが、場合によつてはそれ以上の加圧下でも減圧
下でもよい。
本発明の方法においては、原料の塩化アルキル
および亜硝酸アルカリ金属塩、相間移動触媒、水
および必要に応じて使用する有機溶媒の仕込みの
方法に特に制限はない。
反応後生成物は慣用の蒸留法で反応混合物から
分離し高純度の低級ニトロパラフインを得ること
が出来る。
以下、本発明を実施例により説明する。
実施例 １
200mlの耐圧ガラス反応容器に亜硝酸ナトリウ
ム水溶液4mol／ｌを75mlとり、トルエンを75ml
加え、更にテトラｎ―ブチルアンモニウム8.35ｇ
を加え、反応系内を手速く減圧にして脱気を行な
い、氷水で冷却して塩化メチル35ｇを導入した。
反応器内容物は完全に二相に分離していた。氷水
浴をはずし撹拌を開始した。この時圧力は１Kg／
cm2ゲージを示していた。室温で撹拌を3.5時間続
けた後、反応容器を開放し、ゆるやかに撹拌しな
がら過剰の塩化メチルを気体として除去した。反
応混合物を分液ロートに移し、有機相と水相とに
分離し、水相をトルエンで洗浄した。この有機相
とトルエン洗浄液とにそれぞれ含まれるニトロメ
タンの量をガスクロマトグラフイーで定量した。
一方有機相は水で洗浄し、水相とこの水洗浄液と
に含まれる亜硝酸ナトリウムの量を、酸性過マン
ガン酸カリウム溶液中へ試料を滴下する亜硝酸塩
の慣用の滴定法により、定量した。以上の結果、
転化した亜硝酸ナトリウムは仕込んだものの12％
（転化率）であり、転化した亜硝酸ナトリウムに
対するニトロメタンの生成率、すなわち選択率は
84％であつた。亜硝酸メチルエステルおよび亜硝
酸メチルエステルの加水分解で生成するであろう
メタノールの生成は認められなかつた。未反応の
亜硝酸ナトリウムとニトロメタンの合計のモル数
は、仕込んだ亜硝酸カリウムに対して98％（回収
率）であつた。
実施例 ２
相間移動触媒をトリオクチルメチルアンモニウ
ムクロライドにかえたほかは実施例１と全く同様
の方法で反応を行なつたところ亜硝酸ナトリウム
の転化率は9.8％でありニトロメタンの選択率は
72％であつた。メタノールの生成が微量認められ
た。未反応亜硝酸ナトリウム、ニトロメタンおよ
び微量のメタノールの合計モル数は、仕込んだ亜
硝酸ナトリウムの96％であつた。A quaternary pyridinium salt or a quaternary salt of a pyridine analog represented by the formula (where R 1 , R 2 and
Examples include dodecylpyridinium chloride and 1-ethylquinolinium chloride. (c) General formula R 1 , R 2 , R 3 , R 4 , P, X (here, R 1 , R 2 ,
Quaternary phosphonium salts represented by R 3 , R 4 and (d) General formula R 1・R 2・R 3・R 4・As・X (here, R 1 ,
R 2 , R 3 , R 4 and X are the same as above), such as a quaternary arsonium salt such as tetraphenyl arsonium chloride. Furthermore, (e) macrocyclic polyethers, so-called crown ethers, such as dicyclohexyl-18-crown-6, and polycyclic macrocyclic polyaminoethers, so-called cryptands, can also be used. These phase transfer catalysts transfer only the anion moiety, that is, the nitro group, of the alkali metal nitrite salt from the aqueous phase to the organic phase where alkyl chloride is present, through the process of ion exchange reaction in the aqueous phase, or
Alternatively, it functions to transfer the alkali metal nitrite salt from the aqueous phase to the organic phase as a complex through a complex formation reaction process in the aqueous phase. The amount of these phase transfer catalysts used in the method of the present invention is not particularly limited, but is usually 0.001 to 1 mole of the alkali metal nitrite salt used.
~1 mole. The reaction temperature in the method of the present invention is 5 to 90°C, preferably 15 to 40°C, and usually room temperature. The reaction pressure is usually between normal pressure and 5 kg/cm 2 G, but it may be under higher pressure or under reduced pressure depending on the case. In the method of the present invention, there are no particular limitations on the method of charging the raw materials alkyl chloride and alkali metal nitrite, phase transfer catalyst, water, and an organic solvent used as necessary. The reaction product can be separated from the reaction mixture by a conventional distillation method to obtain a highly pure lower nitroparaffin. The present invention will be explained below using examples. Example 1 Place 75 ml of a 4 mol/l sodium nitrite aqueous solution in a 200 ml pressure-resistant glass reaction vessel, and add 75 ml of toluene.
In addition, 8.35g of tetra n-butylammonium
was added, the reaction system was quickly depressurized for degassing, cooled with ice water, and 35 g of methyl chloride was introduced.
The reactor contents were completely separated into two phases. The ice water bath was removed and stirring was started. At this time the pressure is 1Kg/
It showed cm2 gauge. After continued stirring at room temperature for 3.5 hours, the reaction vessel was opened and excess methyl chloride was removed as a gas with gentle stirring. The reaction mixture was transferred to a separatory funnel and separated into an organic phase and an aqueous phase, and the aqueous phase was washed with toluene. The amount of nitromethane contained in this organic phase and the toluene washing solution was determined by gas chromatography.
Meanwhile, the organic phase was washed with water, and the amount of sodium nitrite contained in the aqueous phase and the water wash was determined by a conventional titration method for nitrite, in which the sample was dropped into an acidic potassium permanganate solution. As a result of the above,
Converted sodium nitrite is 12% of the charged amount
(conversion rate), and the production rate of nitromethane with respect to converted sodium nitrite, that is, the selectivity is
It was 84%. The production of nitrite methyl ester and methanol that would be produced by hydrolysis of nitrite methyl ester was not observed. The total number of moles of unreacted sodium nitrite and nitromethane was 98% (recovery rate) of the charged potassium nitrite. Example 2 A reaction was carried out in exactly the same manner as in Example 1 except that the phase transfer catalyst was changed to trioctylmethylammonium chloride. The conversion rate of sodium nitrite was 9.8% and the selectivity of nitromethane was
It was 72%. A trace amount of methanol was observed. The total number of moles of unreacted sodium nitrite, nitromethane, and trace amounts of methanol was 96% of the charged sodium nitrite.
Claims (1)
酸アルカリ金属塩とを反応させ対応する低級ニト
ロパラフイン類を製造するに際し、塩化アルキル
を溶媒に溶解させるかまたは無溶媒のまま有機相
に存在させ、一方、亜硝酸アルカリ金属塩は水溶
液として水相に存在させ、この有機相と水相間に
相間移動触媒を用いて、反応させることを特徴と
する低級ニトロパラフイン類の製造法。1. When producing the corresponding lower nitroparaffins by reacting a lower alkyl chloride having 1 to 3 carbon atoms with an alkali metal nitrite salt, the alkyl chloride is dissolved in a solvent or left in the organic phase without a solvent. , on the other hand, a method for producing lower nitroparaffins, characterized in that an alkali metal nitrite salt is present as an aqueous solution in an aqueous phase, and a phase transfer catalyst is used to cause a reaction between the organic phase and the aqueous phase.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7373980A JPS56169648A (en) | 1980-06-03 | 1980-06-03 | Preparation of lower nitroparaffins |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7373980A JPS56169648A (en) | 1980-06-03 | 1980-06-03 | Preparation of lower nitroparaffins |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS56169648A JPS56169648A (en) | 1981-12-26 |
| JPS6250459B2 true JPS6250459B2 (en) | 1987-10-24 |
Family
ID=13526902
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP7373980A Granted JPS56169648A (en) | 1980-06-03 | 1980-06-03 | Preparation of lower nitroparaffins |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS56169648A (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4424385A (en) * | 1982-08-02 | 1984-01-03 | W. R. Grace & Co. | Synthesis of nitromethane |
| KR101183822B1 (en) * | 2009-12-18 | 2012-09-19 | 한국화학연구원 | Preparing method of nitroparaffin using solid acidic catalyst |
| KR101178942B1 (en) * | 2010-03-22 | 2012-08-31 | 한국화학연구원 | Preparing method of Nitroparaffin |
| WO2013025061A2 (en) * | 2011-08-17 | 2013-02-21 | 한국화학연구원 | Method for preparing nitroparaffin by gas phase nitration |
-
1980
- 1980-06-03 JP JP7373980A patent/JPS56169648A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS56169648A (en) | 1981-12-26 |
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