JPS6151574B2 - - Google Patents
Info
- Publication number
- JPS6151574B2 JPS6151574B2 JP1813278A JP1813278A JPS6151574B2 JP S6151574 B2 JPS6151574 B2 JP S6151574B2 JP 1813278 A JP1813278 A JP 1813278A JP 1813278 A JP1813278 A JP 1813278A JP S6151574 B2 JPS6151574 B2 JP S6151574B2
- Authority
- JP
- Japan
- Prior art keywords
- nitrite
- dicyclohexyl
- caprolactam
- cyclohexanone
- mole
- 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
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 claims description 19
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 20
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 14
- VEZUQRBDRNJBJY-UHFFFAOYSA-N cyclohexanone oxime Chemical compound ON=C1CCCCC1 VEZUQRBDRNJBJY-UHFFFAOYSA-N 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 8
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- AFLQDEOAJRGCOW-UHFFFAOYSA-N nitrosocyclohexane Chemical compound O=NC1CCCCC1 AFLQDEOAJRGCOW-UHFFFAOYSA-N 0.000 description 5
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 4
- 239000004157 Nitrosyl chloride Substances 0.000 description 4
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 4
- 239000000539 dimer Substances 0.000 description 4
- 238000002329 infrared spectrum Methods 0.000 description 4
- 239000000543 intermediate Substances 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- VPCDQGACGWYTMC-UHFFFAOYSA-N nitrosyl chloride Chemical compound ClN=O VPCDQGACGWYTMC-UHFFFAOYSA-N 0.000 description 4
- 235000019392 nitrosyl chloride Nutrition 0.000 description 4
- 239000003208 petroleum Substances 0.000 description 4
- 230000008707 rearrangement Effects 0.000 description 4
- 238000000921 elemental analysis Methods 0.000 description 3
- 238000001819 mass spectrum Methods 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- LZDSILRDTDCIQT-UHFFFAOYSA-N dinitrogen trioxide Chemical compound [O-][N+](=O)N=O LZDSILRDTDCIQT-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- DTTDXHDYTWQDCS-UHFFFAOYSA-N 1-phenylcyclohexan-1-ol Chemical compound C=1C=CC=CC=1C1(O)CCCCC1 DTTDXHDYTWQDCS-UHFFFAOYSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-N Nitrous acid Chemical compound ON=O IOVCWXUNBOPUCH-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 238000001103 continuous-wave nuclear magnetic resonance spectrum Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- HHNHBFLGXIUXCM-GFCCVEGCSA-N cyclohexylbenzene Chemical compound [CH]1CCCC[C@@H]1C1=CC=CC=C1 HHNHBFLGXIUXCM-GFCCVEGCSA-N 0.000 description 1
- 230000000447 dimerizing effect Effects 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- WVQMNVHWDSLKKT-UHFFFAOYSA-N n-cyclohexylidenehydroxylamine;hydrochloride Chemical compound Cl.ON=C1CCCCC1 WVQMNVHWDSLKKT-UHFFFAOYSA-N 0.000 description 1
- -1 nitrite ester Chemical class 0.000 description 1
- NJNQUTDUIPVROZ-UHFFFAOYSA-N nitrocyclohexane Chemical compound [O-][N+](=O)C1CCCCC1 NJNQUTDUIPVROZ-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
本発明は、式
で示される亜硝酸1―ジシクロヘキシルに関する
ものである。
亜硝酸1―ジシクロヘキシルはε―カプロラク
タムの中間体として有用である。すなわち、亜硝
酸1―ジシクロヘキシルは熱分解によりシクロヘ
キサノンとニトロソシクロヘキサンの二量体を生
成する。シクロヘキサノンはヒドロキシルアミン
と反応させてシクロヘキサノンオキシムとした
後、ベツクマン転位によりε―カプロラクタムが
得られること、またニトロソシクロヘキサンの二
量体は異性化してシクロヘキサノンオキシムとし
た後、ベツクマン転位によりε―カプロラクタム
が得られることが知られている。
現在、ベンゼンを原料とするε―カプロラクタ
ムの工業的製法の代表的なものとして、シクロヘ
キサンを光の存在下に塩化ニトロシルと反応させ
てシクロヘキサノンオキシム塩酸塩とし、ベツク
マン転位によりε―カプロラクタムを得る方法、
およびシクロヘキサンを液相酸化してシクロヘキ
サノンを得、これをヒドロキシルアミンと反応さ
せてシクロヘキサノンオキシムとした後、ベツク
マン転位によりε―カプロラクタムを得る方法が
採用されている。
しかしながら、前者では塩化ニトロシルのよう
に非常に腐食性の強い試薬を使用しなければなら
ず、また比較的高価な光エネルギーを必要とする
という不利な点があり、また後者ではシクロヘキ
サノンに対して少なくとも等モルの比較的高価な
ヒドロキシルアミンを使用しなければならないと
いう不利な点がある。
そこで、本発明者らは、ε―カプロラクタム製
造のための中間体としてシクロヘキサンに代る中
間体について種々探索検討した結果、亜硝酸1―
ジシクロヘキシルが有用であることを見出した。
すなわち、本発明に係る亜硝酸1―ジシクロヘ
キシルからε―カプロラクタムを製造する工程は
次の反応式によつて示される。
この反応式から明らかなように、亜硝酸1―ジ
シクロヘキシルをε―カプロラクタムの中間体と
して使用した場合、現在、工業的に採用されてい
るシクロヘキサンからε―カプロラクタムを得る
方法と比較して、腐食性試薬および光エネルギー
を用いることなく、さらにヒドロキシルアミンの
使用量を約半量に減少させることができるという
利点をもつている。
すなわち、従来法によれば1モルのシクロヘキ
サノンオキシムを得るのに1モルのヒドロキシル
アミンを必要としていた。これに対して、亜硝酸
1―ジシクロヘキシルを用いると、1モルの亜硝
酸1―ジシクロヘキシル()は1モルのシクロ
ヘキサノン()と1/2モルのニトロソシクロヘキ
サン二量体()に熱分解され、()からはア
ルコール溶媒中、加熱することによる異性化によ
つて1モルのシクロヘキサノンオキシム()が
得られ、一方の()からは1モルのヒドロキシ
ルアミンとの反応によつて1モルのシクロヘキサ
ノンオキシム()が得られる。つまり、2モル
のシクロヘキサノンオキシムを得るのに1モルの
ヒドロキシルアミンしか必要としない。
本発明に係る亜硝酸1―ジシクロヘキシルは1
―ジシクロヘキサノールを塩化ニトロシルまたは
三酸化二窒素と反応させることにより合成され
る。またこの1―ジシクロヘキサノールはベンゼ
ンを水素添加、二量化してシクロヘキシルベンゼ
ンに変換し、ついでこれを酸化して1―ヒドロキ
シシクロヘキシルベンゼンに変換し、ついでこれ
を水素添加することにより合成される。
次に、本発明に係る亜硝酸1―ジシクロヘキシ
ルの合成例について具体的に説明する。
1―ジシクロヘキサノール9.35gをピリジン50
mlに溶解し、氷冷下、撹拌しながら、これに塩化
ニトロシル4.0gを気体状で窒素ガスをキヤリヤ
ーガスとして1時間10分を要して通気し、反応さ
せた。ついで室温で2時間撹拌し、反応生成物に
石油エーテルおよび水を各100ml徐々に加えた。
石油エーテル層を分離後、この層を水および1/
10規定塩酸で洗浄し、無水硫酸ナトリウムを加え
乾燥した。ついで石油エーテル層から石油エーテ
ルを回収除去した後、残渣を減圧蒸留した。沸点
75〜92℃/0.4mmHgの黄色液体9.96g(収率92
%)を得た。これを再蒸留して沸点91〜92℃/
0.4mmHgをもつ黄色液体の亜硝酸1―ジシクロヘ
キシルを得た。
実施例
亜硝酸1―ジシクロヘキシルの構造確認は元素
分析、IRスペクトル、NMR吸収スペクトル、お
よびマススペクトルにより行い、確認した。
(i) 元素分析
元素分析値
C H N
計算値(%) 68.21 10.02 6.63
実測値(%) 68.05 9.89 6.41
以上のようにC12H21NO2としての計算した値と
実測値とはよく一致した。
(ii) IRスペクトル
第1図に示すように、2940,2860,および1440
cm-1にシクロヘキサン環のメチレン基に基づく特
性吸収、また1625,815,790、および750cm-1に
亜硝酸エステルのN―O結合に基づく特性吸収を
示す。これによつてシクロヘキサン環と亜硝酸エ
ステル基の存在が確認された。
(iii) NMRスペクトル
第2図に示すように、δ値1.54ppmを中心にし
て0.80〜2.30ppmにシクロヘキサン環のプロトン
に基づく多重線ピークを示し、これ以外のピーク
は示さない。これによつてこの化合物中のプロト
ンを含む基はシクロヘキサン環だけであることが
確認された。
(iv) マススペクトル
第3図に示すように、m/e212にM+1に対応
するピーク、またm/e181と165に
The present invention is based on the formula This relates to 1-dicyclohexyl nitrite represented by 1-Dicyclohexyl nitrite is useful as an intermediate for ε-caprolactam. That is, 1-dicyclohexyl nitrite produces a dimer of cyclohexanone and nitrosocyclohexane by thermal decomposition. Cyclohexanone is reacted with hydroxylamine to form cyclohexanone oxime, and then ε-caprolactam is obtained by Beckman rearrangement, and the dimer of nitrosocyclohexane is isomerized to cyclohexanone oxime, and then ε-caprolactam is obtained by Beckman rearrangement. It is known that Currently, a typical industrial method for producing ε-caprolactam using benzene as a raw material is a method in which cyclohexane is reacted with nitrosyl chloride in the presence of light to form cyclohexanone oxime hydrochloride, and then ε-caprolactam is obtained by Becman rearrangement.
A method has been adopted in which cyclohexanone is obtained by liquid-phase oxidation of cyclohexane, which is reacted with hydroxylamine to form cyclohexanone oxime, and then ε-caprolactam is obtained by Beckman rearrangement. However, the former has the disadvantage of having to use highly corrosive reagents such as nitrosyl chloride and requires relatively expensive light energy; The disadvantage is that equimolar amounts of relatively expensive hydroxylamine must be used. Therefore, the present inventors have searched and studied various intermediates to replace cyclohexane as an intermediate for producing ε-caprolactam, and found that nitrite 1-
We have found dicyclohexyl to be useful. That is, the process of producing ε-caprolactam from 1-dicyclohexyl nitrite according to the present invention is shown by the following reaction formula. As is clear from this reaction formula, when 1-dicyclohexyl nitrite is used as an intermediate for ε-caprolactam, it is more corrosive than the method currently used industrially to obtain ε-caprolactam from cyclohexane. It has the advantage of not using reagents or light energy, and that the amount of hydroxylamine used can be reduced to about half. That is, according to the conventional method, 1 mole of hydroxylamine was required to obtain 1 mole of cyclohexanone oxime. On the other hand, when 1-dicyclohexyl nitrite is used, 1 mole of 1-dicyclohexyl nitrite ( ) is thermally decomposed into 1 mole of cyclohexanone ( ) and 1/2 mole of nitrosocyclohexane dimer ( ) gives 1 mole of cyclohexanone oxime ( ) by isomerization by heating in an alcoholic solvent, and from one ( ), 1 mole of cyclohexanone oxime ( ) is obtained by reaction with 1 mole of hydroxylamine. ) is obtained. That is, only 1 mole of hydroxylamine is required to obtain 2 moles of cyclohexanone oxime. The 1-dicyclohexyl nitrite according to the present invention is 1
-Synthesized by reacting dicyclohexanol with nitrosyl chloride or dinitrogen trioxide. Moreover, this 1-dicyclohexanol is synthesized by hydrogenating and dimerizing benzene to convert it into cyclohexylbenzene, then oxidizing this to convert it into 1-hydroxycyclohexylbenzene, and then hydrogenating this. Next, a synthesis example of 1-dicyclohexyl nitrite according to the present invention will be specifically explained. 9.35 g of 1-dicyclohexanol and 50 g of pyridine
ml, and while stirring under ice-cooling, 4.0 g of nitrosyl chloride was bubbled into the solution in a gaseous state using nitrogen gas as a carrier gas over a period of 1 hour and 10 minutes to cause a reaction. The mixture was then stirred at room temperature for 2 hours, and 100 ml each of petroleum ether and water were gradually added to the reaction product.
After separating the petroleum ether layer, this layer is mixed with water and 1/2
It was washed with 10N hydrochloric acid and dried by adding anhydrous sodium sulfate. After petroleum ether was then recovered and removed from the petroleum ether layer, the residue was distilled under reduced pressure. boiling point
9.96g of yellow liquid at 75-92℃/0.4mmHg (yield 92
%) was obtained. This is redistilled and the boiling point is 91-92℃/
1-dicyclohexyl nitrite was obtained as a yellow liquid with 0.4 mmHg. Example The structure of 1-dicyclohexyl nitrite was confirmed by elemental analysis, IR spectrum, NMR absorption spectrum, and mass spectrum. (i) Elemental analysis Elemental analysis value C H N Calculated value (%) 68.21 10.02 6.63 Actual value (%) 68.05 9.89 6.41 As shown above, the calculated value and actual measurement value for C 12 H 21 NO 2 were in good agreement. . (ii) IR spectrum As shown in Figure 1, 2940, 2860, and 1440
A characteristic absorption based on the methylene group of the cyclohexane ring is shown at cm -1 , and a characteristic absorption based on the N--O bond of the nitrite ester is shown at 1625, 815, 790, and 750 cm -1 . This confirmed the presence of a cyclohexane ring and a nitrite group. (iii) NMR spectrum As shown in Figure 2, a multiplet peak based on the proton of the cyclohexane ring is shown at 0.80 to 2.30 ppm centered around the δ value of 1.54 ppm, and no other peaks are shown. This confirmed that the only group containing a proton in this compound was the cyclohexane ring. (iv) Mass spectrum As shown in Figure 3, there is a peak corresponding to M+1 at m/e212, and a peak at m/e181 and 165.
【式】と[Formula] and
【式】に
それぞれ対応するピークを示す。これによつて、
この物質はThe peaks corresponding to [Formula] are shown. By this,
This substance is
【式】基を含み、分子
量が211である化合物、すなわち亜硝酸1―ジシ
クロヘキシルであることが確認された。
以上の各スペクトルは次のように測定した。It was confirmed that the compound contained the group [Formula] and had a molecular weight of 211, that is, 1-dicyclohexyl nitrite. Each of the above spectra was measured as follows.
【表】【table】
【表】
参考例
亜硝酸1―ジシクロヘキシルの熱分解によつて
シクロヘキサノンおよびニトロシクロヘキサンの
二量体が合成される実験例を示す。
ガラス製の内径11.5mmの反応管(予熱帯:長さ
70mm、反応帯:長さ180mm)を垂直に保ち、その
上部から一酸化一窒素を53.1ml/minの流速で通
気し、減圧状態になつた試料供給口から亜硝酸1
―ジシクロヘキシル1.07g(5.04ミリモル)とn
―ヘプタン0.51gの混合液を、190℃に保たれた
予熱帯、ついで300℃に保たれた反応帯に導入し
た。亜硝酸1―ジシクロヘキシルの反応帯内の滞
留時間は0.26秒である。反応管下部から流出する
反応生成物を冷却、捕集した。これをガスクロマ
トグラフイーにより分析したところ、シクロヘキ
サノン0.25g(収率51%)およびニトロソシクロ
ヘキサンの二量体0.27g(収率47%)が生成した
ことが確認された。ただし、収率は1モルの原料
から1モルのシクロヘキサノンおよび1モルのニ
トロソシクロヘキサン二量体が生成するとして計
算した。[Table] Reference Example An experimental example is shown in which dimers of cyclohexanone and nitrocyclohexane are synthesized by thermal decomposition of 1-dicyclohexyl nitrite. Glass reaction tube with an inner diameter of 11.5 mm (preparation zone: length
70 mm, reaction zone: length 180 mm) was held vertically, monoxide was aerated from the top at a flow rate of 53.1 ml/min, and 1 nitrous acid was injected from the sample supply port under reduced pressure.
-dicyclohexyl 1.07g (5.04mmol) and n
-A mixture of 0.51 g of heptane was introduced into a preheating zone kept at 190°C and then into a reaction zone kept at 300°C. The residence time of 1-dicyclohexyl nitrite in the reaction zone is 0.26 seconds. The reaction product flowing out from the bottom of the reaction tube was cooled and collected. When this was analyzed by gas chromatography, it was confirmed that 0.25 g of cyclohexanone (yield: 51%) and 0.27 g of a dimer of nitrosocyclohexane (yield: 47%) were produced. However, the yield was calculated assuming that 1 mol of cyclohexanone and 1 mol of nitrosocyclohexane dimer were produced from 1 mol of the raw material.
第1図は亜硝酸1―ジシクロヘキシルのIRス
ペクトル、第2図はそのNMRスペクトル、第3
図はそのマススペクトルをそれぞれ示す。
Figure 1 is the IR spectrum of 1-dicyclohexyl nitrite, Figure 2 is its NMR spectrum, and Figure 3 is the IR spectrum of 1-dicyclohexyl nitrite.
The figures show their mass spectra.
Claims (1)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP1813278A JPS54112843A (en) | 1978-02-21 | 1978-02-21 | 1-dicyclohexyl nitrite |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP1813278A JPS54112843A (en) | 1978-02-21 | 1978-02-21 | 1-dicyclohexyl nitrite |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS54112843A JPS54112843A (en) | 1979-09-04 |
JPS6151574B2 true JPS6151574B2 (en) | 1986-11-10 |
Family
ID=11963070
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP1813278A Granted JPS54112843A (en) | 1978-02-21 | 1978-02-21 | 1-dicyclohexyl nitrite |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS54112843A (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS6413693A (en) * | 1987-07-07 | 1989-01-18 | Laurel Bank Machine Co | Two-way distributor for coin dispenser |
-
1978
- 1978-02-21 JP JP1813278A patent/JPS54112843A/en active Granted
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS6413693A (en) * | 1987-07-07 | 1989-01-18 | Laurel Bank Machine Co | Two-way distributor for coin dispenser |
Also Published As
Publication number | Publication date |
---|---|
JPS54112843A (en) | 1979-09-04 |
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