JPS63196550A - Production of high-purity suberonitrile - Google Patents
Production of high-purity suberonitrileInfo
- Publication number
- JPS63196550A JPS63196550A JP62028193A JP2819387A JPS63196550A JP S63196550 A JPS63196550 A JP S63196550A JP 62028193 A JP62028193 A JP 62028193A JP 2819387 A JP2819387 A JP 2819387A JP S63196550 A JPS63196550 A JP S63196550A
- Authority
- JP
- Japan
- Prior art keywords
- suberonitrile
- dichlorohexane
- distillation
- column
- distillation column
- 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.)
- Granted
Links
- BTNXBLUGMAMSSH-UHFFFAOYSA-N octanedinitrile Chemical compound N#CCCCCCCC#N BTNXBLUGMAMSSH-UHFFFAOYSA-N 0.000 title claims description 33
- 238000004519 manufacturing process Methods 0.000 title claims description 8
- 238000004821 distillation Methods 0.000 claims abstract description 37
- 238000009835 boiling Methods 0.000 claims abstract description 20
- 239000007788 liquid Substances 0.000 claims abstract description 11
- OVISMSJCKCDOPU-UHFFFAOYSA-N 1,6-dichlorohexane Chemical compound ClCCCCCCCl OVISMSJCKCDOPU-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000003054 catalyst Substances 0.000 claims abstract description 8
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 4
- 239000007864 aqueous solution Substances 0.000 claims abstract description 4
- 239000000126 substance Substances 0.000 claims description 17
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 11
- 239000003444 phase transfer catalyst Substances 0.000 abstract description 9
- 239000000047 product Substances 0.000 abstract description 5
- 239000007795 chemical reaction product Substances 0.000 abstract description 4
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 abstract description 2
- 150000004985 diamines Chemical class 0.000 abstract description 2
- 239000003814 drug Substances 0.000 abstract description 2
- 150000001875 compounds Chemical class 0.000 abstract 3
- KXZJHVJKXJLBKO-UHFFFAOYSA-N chembl1408157 Chemical compound N=1C2=CC=CC=C2C(C(=O)O)=CC=1C1=CC=C(O)C=C1 KXZJHVJKXJLBKO-UHFFFAOYSA-N 0.000 abstract 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 abstract 1
- 239000003905 agrochemical Substances 0.000 abstract 1
- 125000005207 tetraalkylammonium group Chemical group 0.000 abstract 1
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000012071 phase Substances 0.000 description 5
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 5
- 238000000746 purification Methods 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000008346 aqueous phase Substances 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- RQXXCWHCUOJQGR-UHFFFAOYSA-N 1,1-dichlorohexane Chemical compound CCCCCC(Cl)Cl RQXXCWHCUOJQGR-UHFFFAOYSA-N 0.000 description 2
- MPPPKRYCTPRNTB-UHFFFAOYSA-N 1-bromobutane Chemical compound CCCCBr MPPPKRYCTPRNTB-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 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 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 238000001577 simple distillation Methods 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- FXBITRHTKQZLRX-UHFFFAOYSA-N 7-chloroheptanenitrile Chemical compound ClCCCCCCC#N FXBITRHTKQZLRX-UHFFFAOYSA-N 0.000 description 1
- 229910001516 alkali metal iodide Inorganic materials 0.000 description 1
- 238000000998 batch distillation Methods 0.000 description 1
- 239000007806 chemical reaction intermediate Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 229910000043 hydrogen iodide Inorganic materials 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は、１．６−ジクロルヘキサンと資化ソーダより
スベロニトリルを製造する方法に関する。DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a method for producing suberonitrile from 1,6-dichlorohexane and sodium assimilate.
スベロニトリルは農医薬品やジカルボン酸、ジアミンな
どの製造用中間体として、有機化学および生物化学の分
野で有用である。Suberonitrile is useful in the fields of organic chemistry and biochemistry as an intermediate for the production of agricultural drugs, dicarboxylic acids, diamines, etc.
（従来の技術）
スベロニトリルの製造方法としては、特開昭６１−１２
２２５８号に１，６−ヘキサンジオールとヨウ化水素ま
たはアルカリ金属のヨウ化物とを反応させて得られた１
、６−ジクロルヘキサンを資化ソーダ、背比カリおよび
青酸などのシアノ化剤と反応させる方法がある。この方
法においては、粗スベロニトリルを疎水性有機溶剤、例
えばエーテル、クロロホルム、酢酸エチル等の溶剤で抽
出し、水洗して、減圧蒸留することにより純度９８％以
上のスベロニトリルを得ている。(Prior art) As a method for producing suberonitrile, JP-A-61-12
No. 2258, 1 obtained by reacting 1,6-hexanediol with hydrogen iodide or an alkali metal iodide
There is a method in which 6-dichlorohexane is reacted with a cyanating agent such as sodium hydroxide, potassium chloride, and hydrocyanic acid. In this method, crude suberonitrile is extracted with a hydrophobic organic solvent such as ether, chloroform, ethyl acetate, etc., washed with water, and distilled under reduced pressure to obtain suberonitrile with a purity of 98% or more.
（発明が解決しようとする問題点）
（Ｒ１””Ｒ４は炭素数が３〜１０のアルキル基を示し
、これらは互いに同一でも異なっていても良い）で表さ
れる相間移動触媒の存在下、１．６−ジクロルヘキサン
と背比ソーダ水溶液を反応させスベロニトリルを製造す
る方法を発明した。(Problems to be Solved by the Invention) In the presence of a phase transfer catalyst represented by (R1""R4 represents an alkyl group having 3 to 10 carbon atoms, and these may be the same or different from each other), We have invented a method for producing suberonitrile by reacting 1.6-dichlorohexane with an aqueous sodium bicarbonate solution.
この方法にによれば、反応生成液は相間移動触媒を使用
することにより、油相と水相に分離し、油相には触媒と
スベロニトリルおよび少量の未反応１．６−ジクロルヘ
キサンと反応中間体の１−シアノ−６−クロルヘキサン
（以下モノニトリルと称する）を含有し、水相には反応
生成物であるＮａＣｊ！および少量の未反応青化ソーダ
が含まれる。According to this method, the reaction product liquid is separated into an oil phase and an aqueous phase by using a phase transfer catalyst, and the oil phase is reacted with the catalyst, suberonitrile, and a small amount of unreacted 1,6-dichlorohexane. The aqueous phase contains the intermediate 1-cyano-6-chlorohexane (hereinafter referred to as mononitrile), and the reaction product NaCj! and a small amount of unreacted cyanide soda.
製品のスベロニトリルは、この油相液を蒸溜することに
より得られる。粗スベロニトリルの蒸留は、ユ、。ニド
１廠。熱分解を−けるため１０〜１５Ｔｏｒｒの減圧下
、２００℃以下の温度で蒸留を行う。The product suberonitrile is obtained by distilling this oil phase liquid. Distillation of crude suberonitrile is performed by: Nido 1 factory. In order to prevent thermal decomposition, distillation is carried out under reduced pressure of 10 to 15 Torr and at a temperature of 200° C. or lower.
蒸留精製は一般に、まず低沸物を除去した後、精スベロ
ニトリルを取り出し、高沸物を釜残として除去する方法
が採られる。この蒸溜法では、加熱により該相関移動触
媒であるテトラブチルアンモニウムプロミド等が一部分
解してトリブチルアミン等となり、製品スベロニトリル
中に混入して品質を損ねることが問題となる。Distillation purification is generally carried out by first removing low-boiling substances, then extracting refined suberonitrile, and removing high-boiling substances as a residue. A problem with this distillation method is that the phase transfer catalyst, such as tetrabutylammonium bromide, is partially decomposed by heating to become tributylamine, etc., which is mixed into the suberonitrile product, impairing its quality.
（問題点を解決するための手段）
発明者等はスベロニトリルを精製する際の以上の如き問
題点を解決すべく鋭意検討した結果、従来一般の蒸溜精
製法で行われる方法、即ち第−蒸溜塔で低沸物を除去し
、第二蒸溜塔で高沸点物を除去する方法に代えて、まず
第−蒸溜塔で高沸物を除去し、次に第二蒸溜塔で低沸物
を除去するようにすれば、第一蒸留塔での加熱によりテ
トラブチルアンモニウムプロミド等が分解して生成する
トリブチルアミンが低沸物として第二蒸溜塔で除去され
、高純度のスベロニトリルが得られることを見出し本発
明に至った。(Means for Solving the Problems) As a result of intensive study to solve the above-mentioned problems when refining suberonitrile, the inventors have developed a method conventionally used in general distillation purification methods, that is, the first distillation column. Instead of removing low-boiling substances in the first distillation column and high-boiling substances in the second distillation column, first remove the high-boiling substances in the first distillation column, and then remove low-boiling substances in the second distillation column. It was discovered that by doing this, tributylamine, which is produced by decomposition of tetrabutylammonium bromide etc. by heating in the first distillation column, can be removed as a low-boiling substance in the second distillation column, and highly pure suberonitrile can be obtained. This led to the present invention.
（Ｒ，〜Ｒ４は炭素数が３〜１０のアルキル基を示し、
これらは互いに同一でも異なっていても良い）で表され
る相間移動触媒の存在下、１，６−ジクロルヘキサンと
背比ソーダ水溶液を反応して得られた粗スベロニトリル
液を蒸留してスベロニトリルを製造するに際し、蒸留塔
を２基設け、まず第−蒸溜塔において該触媒を含む高沸
物を除去し、次に第二蒸溜塔において未反応１．６−ジ
クロルヘキサンを除去することを特徴とする高純度スベ
ロニトリルの製造法である。(R, ~R4 represents an alkyl group having 3 to 10 carbon atoms,
These may be the same or different from each other) In the presence of a phase transfer catalyst represented by During production, two distillation columns are provided, firstly high boiling substances including the catalyst are removed in the first distillation column, and then unreacted 1,6-dichlorohexane is removed in the second distillation column. This is a method for producing high-purity suberonitrile.
本発明で使用される相間移動触媒の例としては、テトラ
プロピルアンモニラプロミド、テトラブチルアンモニウ
ムプロミドなどがある。特にテトラブチルアンモニウム
プロミドが好適である。Examples of phase transfer catalysts used in the present invention include tetrapropylammonila bromide, tetrabutylammonium bromide, and the like. Tetrabutylammonium bromide is particularly suitable.
背比ソーダ水溶液は、工業的に市販されている濃度３０
〜３５χの水溶液をそのまま使用することができ、また
更に必要に応じて濃度を下げて使用することもできる。The aqueous soda solution has a concentration of 30, which is commercially available industrially.
The aqueous solution having a concentration of ~35.chi. can be used as it is, or can be used with a lower concentration if necessary.
本発明において、資化ソーダの使用量は１．６−ジクロ
ルヘキサンに対する資化ソーダのモル比を理論量の２．
０に対し２．１〜２．６程度に若干過剰とすることが好
ましい、２０モル比が低過ぎる場合は収率が低（，１，
６〜ジクロルヘキサンの損失が大きくなる。またこのモ
ル比が高過ぎる場合は排水中にＣＮイオンが残留し、排
水処理の費用が増加する。In the present invention, the amount of sodium assimilate used is 1.6-dichlorohexane at a molar ratio of 2.6-dichlorohexane to the theoretical amount.
It is preferable to have a slight excess of about 2.1 to 2.6 with respect to 0. If the molar ratio of 20 is too low, the yield will be low (,1,
6 - The loss of dichlorohexane becomes large. Furthermore, if this molar ratio is too high, CN ions will remain in the wastewater, increasing the cost of wastewater treatment.
テトラブチルアンモニウムプロミド等の使用量は、１．
６〜ジクロルヘキサン１モル当たり１．５〜１０ｇ、好
ましくは１．５〜６．５ｇとする。テトラブチルアンモ
ニウムプロミド等の使用量が少なすぎると収率が低く、
多い場合は次の精製工程の負荷が太き（なる。The amount of tetrabutylammonium bromide etc. to be used is 1.
6 to 1.5 to 10 g, preferably 1.5 to 6.5 g per mole of dichlorohexane. If the amount of tetrabutylammonium bromide etc. used is too small, the yield will be low;
If the amount is large, the load on the next refining process will be heavy.
反応温度は８０〜１４０℃、好ましくは９０〜１１０℃
とする０反応温度が低いと反応が進行せず、高すぎる場
合は着色や重合の原因となる。Reaction temperature is 80-140°C, preferably 90-110°C
If the reaction temperature is too low, the reaction will not proceed, and if it is too high, it will cause discoloration or polymerization.
反応圧力は特に制限が無いが、通常は常圧で行う０反応
時間は通常０．５〜８ ｈｒ、好ましくは２〜４ ｈｒ
である。The reaction pressure is not particularly limited, but the reaction time is usually 0.5 to 8 hr, preferably 2 to 4 hr, which is usually carried out at normal pressure.
It is.
反応生成液は常温まで冷却することにより、上層の油相
液と下層の水相液に分離、する。油相液には製品のスベ
ロニトリルと反応中間体のモノニトリルおよび触媒が含
まれ、これを２基の蒸留塔で蒸留することにより、高純
度のスベロニトリルが得られる。第一蒸留塔では触媒を
含む高沸物を除去し、第二蒸留塔では低沸物を除去する
。By cooling the reaction product liquid to room temperature, it is separated into an upper oil phase liquid and a lower aqueous phase liquid. The oil phase liquid contains suberonitrile as a product, mononitrile as a reaction intermediate, and a catalyst, and by distilling this in two distillation columns, highly pure suberonitrile can be obtained. The first distillation column removes high-boiling substances including the catalyst, and the second distillation column removes low-boiling substances.
第−蒸溜塔および第二蒸溜塔において、前述の如くスベ
ロニトリルの熱分解を避けるため液温を２００″Ｃ以下
、好ましくは１８０°Ｃ以下とする。またこのため圧力
は１〜４０Ｔｏｒｒ、好ましくは１〜１５Ｔ。In the first distillation column and the second distillation column, the liquid temperature is kept at 200"C or less, preferably 180"C or less, to avoid thermal decomposition of suberonitrile as described above. Also, for this purpose, the pressure is set at 1 to 40 Torr, preferably 180"C or less. ~15T.
ｒｒとする。圧力が高すぎれば、塔底の温度が高くなり
スベロニトリルが分解し回収率が低下する。Let it be rr. If the pressure is too high, the temperature at the bottom of the column will increase, decomposing the suberonitrile, and reducing the recovery rate.
圧力がこれより低くても良いが蒸溜塔が太き（なるので
経済的でない。各蒸溜塔は段塔でも充填塔でも良いが、
理論段数として第−蒸溜塔では１段で良く、第二蒸溜塔
では蒸留条件によるが５〜５０段、好ましくは１５〜３
０段とする。還流比は第−蒸溜塔ではＯ〜５、好ましく
はＯ〜１であり、第二蒸溜塔では５〜２０、好ましくは
５〜１０である。Although the pressure may be lower than this, it is not economical because the distillation column will be thick.Each distillation column may be a plated column or a packed column, but
The number of theoretical plates may be 1 in the first distillation column, and 5 to 50, preferably 15 to 3, depending on the distillation conditions in the second distillation column.
Set to 0 stage. The reflux ratio is 0 to 5, preferably 0 to 1 in the first distillation column, and 5 to 20, preferably 5 to 10 in the second distillation column.
（作用および効果）
本発明によれば、相間移動触媒であるテトラブチルアン
モニウムプロミド等が分解することにより生成するトリ
ブチルアミン等が製品中に混入することなく高純度のス
ベロニトリルが得られる。(Functions and Effects) According to the present invention, highly pure suberonitrile can be obtained without contaminating the product with tributylamine, etc., which are generated by decomposition of tetrabutylammonium bromide, which is a phase transfer catalyst.
本方法においては工業的に安価に得られる１、６−ジク
ロルヘキサンを原料としており、且つ反応工程および精
製工程が非常に簡略なプロセスで高純度のスベロニトリ
ルが得られるので、本発明の工業的意義が大きい。In this method, 1,6-dichlorohexane, which can be obtained industrially at low cost, is used as a raw material, and highly pure suberonitrile can be obtained through a very simple reaction and purification process. It has great significance.
（実施例） 次に実施例を用い本発明を具体的に説明する。(Example) Next, the present invention will be specifically explained using Examples.
比較例は、従来一般の蒸留精製法で行われる方法、即ち
まず低沸物を除去し、次に高沸物を除去する方法による
場合とし、本発明の方法による実施例と対比した。Comparative examples were conducted using a conventional distillation purification method, that is, first removing low-boiling substances and then removing high-boiling substances, and were compared with examples using the method of the present invention.
叉旌拠よ
相間移動触媒としてテトラブチルアンモニウムプロミド
を用い、１．６−ジクロルヘキサンに対する背比ソーダ
のモル比を２．１、触媒量を１．６−ジクロルヘキサン
１モル当たり３．３ｇとし、常圧下反応温度１１０°Ｃ
で４時間反応させ、冷却により分離しり粗スベロニトリ
ル液１０１００Ｏスベロニトリル濃度８４χ）を、圧力
１０Ｔｏｒｒ温度１８０″Ｃで単蒸留により高沸物を除
去し、留出液９５０ｇ （スベロニトリル濃度８７χ）
を得た。この留出液を上部に３０段相当の充填物を有す
る蒸留釜を用い頂部圧力５Ｔｏｒｒ （釜内１５Ｔ。In this case, tetrabutylammonium bromide was used as a phase transfer catalyst, the molar ratio of soda to 1.6-dichlorohexane was 2.1, and the amount of catalyst was 3.5% per mole of 1.6-dichlorohexane. 3g, reaction temperature 110°C under normal pressure
The crude suberonitrile liquid (10100O suberonitrile concentration 84χ) was separated by cooling for 4 hours, and the high-boiling substances were removed by simple distillation at a pressure of 10 Torr and a temperature of 180''C to obtain 950 g of distillate (suberonitrile concentration 87χ).
I got it. This distillate was poured into a distillation pot with packing equivalent to 30 stages at the top, and the pressure at the top was 5 Torr (15T inside the pot).
ｒｒ）還流比５．０で回分蒸留を行い、低沸留出液１３
０ｇを得た。この蒸留時の温度は、頂部５３〜１６０°
Ｃ１釜内１６７〜１９０°Ｃであった。この結果、純度
９９．０％以上の精スベロニトリルが８２０ｇ得られ、
精スベロニトリル中にトリブチルアミンおよびブチルプ
ロミドが検出されなかった。rr) Perform batch distillation at a reflux ratio of 5.0 to obtain a low-boiling distillate 13
Obtained 0g. The temperature during this distillation is 53° to 160° at the top.
The temperature inside the C1 pot was 167-190°C. As a result, 820g of purified suberonitrile with a purity of 99.0% or more was obtained,
No tributylamine or butylbromide was detected in the refined suberonitrile.
ル較■上
実施例１と同様にして得られた粗スベロニトリル液１０
００ｇ （スベロニトリル濃度８３．Ｏχ）を、実施例
１と同じ３０段相当の蒸留釜を用い回分蒸留し、低。10 Crude suberonitrile liquid obtained in the same manner as in Example 1
00g (suberonitrile concentration 83.Ox) was batch distilled using the same 30-plate distillation pot as in Example 1, and the concentration was 83.Ox.
沸留出液１１０ｇを得た。この時の還流比は５．０とし
、圧力は頂部２Ｔｏｒｒ、釜内１０Ｔｏｒｒであり、温
度は頂部４２〜１４０°Ｃ１釜内１５６〜１７３°Ｃで
あった。この蒸留により得られた釜残液８８０ｇ （ス
ベロニトリル濃度９１．５χ）を、圧力１０Ｔｏｒｒ、
温度１８０℃で単蒸留することにより、精スベロニトリ
ル８１０ｇが得られたが、その純度は９８．４χであり
、トリブチルアミン０．９７χ、ブチルプロミド０．２
４χが検出された。110 g of boiling distillate was obtained. The reflux ratio at this time was 5.0, the pressure was 2 Torr at the top and 10 Torr inside the pot, and the temperature was 42-140°C at the top and 156-173°C inside the pot. 880 g of the pot residue obtained by this distillation (suberonitrile concentration 91.5χ) was heated at a pressure of 10 Torr.
By simple distillation at a temperature of 180°C, 810 g of refined suberonitrile was obtained, the purity of which was 98.4χ, tributylamine 0.97χ, butylbromide 0.2
4χ was detected.
Claims (1)
１〜Ｒ＿４は炭素数が３〜１０のアルキル基を示し、こ
れらは互に同じでも異なっていても良い）で表される相
間移動触媒の存在下、１，６−ジクロルヘキサンと青化
ソーダ水溶液を反応させて得られた粗スベロニトリル液
を蒸留してスベロニトリルを製造するに際し、蒸留塔を
２基設け、まず第一蒸溜塔において該触媒を含む高沸物
を除去し、次に第二蒸溜塔において未反応１，６−ジク
ロルヘキサンを含む低沸物を除去することを特徴とする
高純度スベロニトリルの製造法[Claims] The general formula is [▲There are mathematical formulas, chemical formulas, tables, etc.▼] (R_
1 to R_4 represent an alkyl group having 3 to 10 carbon atoms, and these may be the same or different.) 1,6-dichlorohexane and soda cyanide. When producing suberonitrile by distilling the crude suberonitrile liquid obtained by reacting an aqueous solution, two distillation columns are installed, and the first distillation column first removes high boiling substances including the catalyst, and then the second distillation column removes high boiling substances including the catalyst. A method for producing high-purity suberonitrile, characterized by removing low-boiling substances including unreacted 1,6-dichlorohexane in a column
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62028193A JPH0832671B2 (en) | 1987-02-12 | 1987-02-12 | Method for producing high-purity suberonitrile |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62028193A JPH0832671B2 (en) | 1987-02-12 | 1987-02-12 | Method for producing high-purity suberonitrile |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63196550A true JPS63196550A (en) | 1988-08-15 |
| JPH0832671B2 JPH0832671B2 (en) | 1996-03-29 |
Family
ID=12241843
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62028193A Expired - Lifetime JPH0832671B2 (en) | 1987-02-12 | 1987-02-12 | Method for producing high-purity suberonitrile |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0832671B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0860427A1 (en) * | 1997-02-25 | 1998-08-26 | Basf Aktiengesellschaft | Process for the removal of halides from halide containing nitrile mixtures |
-
1987
- 1987-02-12 JP JP62028193A patent/JPH0832671B2/en not_active Expired - Lifetime
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0860427A1 (en) * | 1997-02-25 | 1998-08-26 | Basf Aktiengesellschaft | Process for the removal of halides from halide containing nitrile mixtures |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0832671B2 (en) | 1996-03-29 |
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