CN102351712B - N-苯基四氢-2-萘胺的制备方法 - Google Patents
N-苯基四氢-2-萘胺的制备方法 Download PDFInfo
- Publication number
- CN102351712B CN102351712B CN2011102505562A CN201110250556A CN102351712B CN 102351712 B CN102351712 B CN 102351712B CN 2011102505562 A CN2011102505562 A CN 2011102505562A CN 201110250556 A CN201110250556 A CN 201110250556A CN 102351712 B CN102351712 B CN 102351712B
- Authority
- CN
- China
- Prior art keywords
- phenyl
- preparation
- reaction
- naphthylamines
- naphthylamine
- 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.)
- Active
Links
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- LSDXVUJCUPTXIN-UHFFFAOYSA-N n-phenyl-1,2,3,4-tetrahydronaphthalen-2-amine Chemical compound C1CC2=CC=CC=C2CC1NC1=CC=CC=C1 LSDXVUJCUPTXIN-UHFFFAOYSA-N 0.000 title abstract 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 49
- KEQFTVQCIQJIQW-UHFFFAOYSA-N N-Phenyl-2-naphthylamine Chemical compound C=1C=C2C=CC=CC2=CC=1NC1=CC=CC=C1 KEQFTVQCIQJIQW-UHFFFAOYSA-N 0.000 claims abstract description 22
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 20
- 238000010438 heat treatment Methods 0.000 claims abstract description 6
- 239000002994 raw material Substances 0.000 claims abstract description 6
- 239000002904 solvent Substances 0.000 claims abstract description 5
- 239000003586 protic polar solvent Substances 0.000 claims abstract description 4
- 239000007788 liquid Substances 0.000 claims description 11
- 229910052739 hydrogen Inorganic materials 0.000 claims description 10
- 239000001257 hydrogen Substances 0.000 claims description 10
- 239000012043 crude product Substances 0.000 claims description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- 239000003880 polar aprotic solvent Substances 0.000 claims description 6
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 238000001514 detection method Methods 0.000 claims description 3
- 238000000746 purification Methods 0.000 claims description 2
- 230000002829 reductive effect Effects 0.000 claims description 2
- 238000007670 refining Methods 0.000 abstract description 6
- 238000000034 method Methods 0.000 abstract description 5
- 230000008901 benefit Effects 0.000 abstract description 3
- 239000003054 catalyst Substances 0.000 abstract description 3
- 238000009903 catalytic hydrogenation reaction Methods 0.000 abstract 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 10
- 238000001816 cooling Methods 0.000 description 7
- 229910052759 nickel Inorganic materials 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 230000008859 change Effects 0.000 description 4
- 238000002425 crystallisation Methods 0.000 description 4
- 230000008025 crystallization Effects 0.000 description 4
- 239000012065 filter cake Substances 0.000 description 4
- 239000000706 filtrate Substances 0.000 description 4
- 150000002431 hydrogen Chemical class 0.000 description 4
- 238000007789 sealing Methods 0.000 description 4
- 239000006228 supernatant Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 238000011010 flushing procedure Methods 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- -1 methoxyl group Chemical group 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- 239000003905 agrochemical Substances 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- ZYIFLKPDFLWFAE-UHFFFAOYSA-N aniline;toluene Chemical compound CC1=CC=CC=C1.NC1=CC=CC=C1 ZYIFLKPDFLWFAE-UHFFFAOYSA-N 0.000 description 1
- FUSUHKVFWTUUBE-UHFFFAOYSA-N buten-2-one Chemical compound CC(=O)C=C FUSUHKVFWTUUBE-UHFFFAOYSA-N 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000001143 conditioned effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical compound C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- GGMJJPPYEFOAHJ-UHFFFAOYSA-N n-phenyl-1,2,3,4-tetrahydronaphthalen-1-amine Chemical compound C12=CC=CC=C2CCCC1NC1=CC=CC=C1 GGMJJPPYEFOAHJ-UHFFFAOYSA-N 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 108091008695 photoreceptors Proteins 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 238000010792 warming Methods 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
- Y02P20/584—Recycling of catalysts
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
一种N-苯基四氢-2-萘胺的制备方法，以N-苯基-2-萘胺为原料，在极性质子溶剂中，加热条件下进行反应。极性质子溶剂为甲醇或乙醇。反应温度范围为：90℃～120℃。以Raney Ni为催化剂进行催化加氢反应。精制溶剂优选甲醇，精制含量大于99%。本发明特点优点：采用本发明方法，反应收率相对较高，催化剂可以循环使用，产品纯度高，“三废”产生少，反应容易控制，精制简单，原材料成本低等优点。
Description
技术领域
本发明涉及可作为医药、农药中间体及电子感光材料使用的N-苯基四氢-2-萘胺的制备方法。
背景技术
N-苯基四氢-2-萘胺可用于制造电子照相感光器，电致发光装置，电荷转移试剂，多用于电子成像领域；也可作为合成聚合亚硝化试剂的单体，由于具有较高的活性而广泛应用于农药、医药等行业。
N-苯基四氢-2-萘胺的制备方法目前是：以2-（苯磺酰基）环己酮与丁烯酮以二氯甲烷作溶剂经长时间反应生成中间体2-(3-酮丁基)-2-(苯磺酰基)环己酮，再与苯胺在对甲苯磺酸催化下回流条件反应，甲苯做溶剂，回流反应得到产品，收率30%。该路线原料不宜购买，反应时间长，操作复杂，收率低。（J.Org.Chem.2009，74，7781-7789）
发明内容
本发明提供一种N-苯基四氢-2-萘胺的制备方法：以N-苯基-2-萘胺为原料，首先在极性质子溶剂中，催化剂Raney Ni催化加氢，升温反应得到粗品。经甲醇精制后得N-苯基四氢-2-萘胺，纯度大于99%。
因此，本发明为了提高反应收率，降低生产危险进行了认真探讨和设计，结果是N-苯基-2-萘胺在极性质子溶剂中（甲醇，乙醇），Raney Ni催化下加氢升温反应得到N-苯基四氢萘胺，精制后得到N-苯基四氢-2-萘胺含量大于99%，收率50%。在提高反应收率的基础上改善生产过程。
本发明具体内容
一种N-苯基四氢-2-萘胺的制备方法，其特征在于，以N-苯基-2-萘胺为原料，氢气为还原剂，Raney Ni为催化剂，于高压釜中极性质子溶剂中加热条件下反应得到粗品，再经提纯后得到精品。
所述极性质子溶剂为甲醇或乙醇。
所述加热反应温度范围为：90℃～120℃。
提纯溶剂优选甲醇，精制后经液相色谱检测质量含量大于99%。
本发明特点优点：
采用本发明方法，反应收率相对较高，催化剂可以循环使用，产品纯度高，“三废”产生少，反应容易控制，精制简单，原材料成本低等优点。
具体实施方式
本发明涉及N-苯基四氢-2-萘胺的制备方法，该方法的特征在于，在极性质子溶剂中，N-苯基-2-萘胺在催化剂催化下加氢还原，加热条件下反应，得到N-苯基四氢-2-萘胺，这里极性质子溶剂优选甲醇，乙醇。反应温度95℃～105℃，优选95℃～100℃。催化剂优选RaneyNi。
本发明的最佳实施方式
工业领域中，N-苯基四氢-2-萘胺的制备方法可按照本发明者开发的方法，最好利用N-苯基-2-萘胺在极性质子溶剂—甲醇或乙醇中，经催化下升温加氢还原，得到N-苯基四氢-2-萘胺粗品。对该方法进行详述，最好使用甲醇或乙醇作为反应溶剂，催化剂优选金属镍或钯碳。另外，反应温度范围反应温度95℃～105℃，优选95℃～100℃。
另外，本发明还可以用于含有甲基，甲氧基，氨基等基团的类似化合物的加氢还原反应。
实施例
以下，通过实施例对本发明进行更详细说明。收率以摩尔百分数表示。
实施例1
向5L的高压釜中加入1公斤N-苯基-2-萘胺与0.12公斤RaneyNi，1.6公斤甲醇，密封高压釜，用氢气排空2次，放置30min后通入6MPa，升温到100℃反应至氢气压力不再变化。将反应液取上层清液，下层的镍继续套用，过滤。滤液蒸出50%，室温搅拌冷却，析晶，降温到10℃以下，过滤，滤饼用少量甲醇冲洗抽干得粗品0.58公斤，液相含量97.5%，收率：57%。
实施例2
向5L的高压釜中加入1公斤N-苯基-2-萘胺与0.12公斤RaneyNi（回收套用）1.6公斤甲醇，密封高压釜，用氢气排空2次，放置30min后通入6MPa，升温到100℃反应至氢气压力不再变化。降温，泄压。将反应液取上层清液，下层的镍继续套用，过滤。将滤液蒸出50%，室温搅拌冷却，析晶。降温到10℃以下，过滤，滤饼用少量甲醇冲洗抽干得粗品0.56公斤，液相含量97.1%，收率：55%。
实施例3
向5L的高压釜中加入1公斤N-苯基-2-萘胺与0.12公斤Raney Ni1.6公斤乙醇，密封高压釜，用氢气排空2次，放置30min后通入6MPa，升温到100℃反应至原料氢气压力不再变化。降温，泄压。将反应液取上层清液，下层的镍继续套用，过滤。将滤液蒸出50%，室温搅拌冷却，析晶。降温到10℃以下，过滤，滤饼用少量乙醇冲洗抽干得粗品0.53公斤，液相含量97.6%，收率：52%。
实施例4
向5L的高压釜中加入1公斤N-苯基-2-萘胺与0.12公斤Raney Ni（回收套用）1.6公斤乙醇，密封高压釜，用氢气排空2次，放置30min后通入6MPa，升温到100℃反应至氢气压力不再变化。降温，泄压。将反应液取上层清液，下层的镍继续套用，过滤。将滤液蒸出50%，室温搅拌冷却，析晶。降温到10℃以下，过滤，滤饼用少量乙醇冲洗抽干得粗品0.519公斤，液相含量97.23%，收率：51%。
实施例5
0.58公斤N-苯基四氢-2-萘胺粗品，加入0.93公斤甲醇，升温至回流搅拌2小时后降温至0℃以下，搅拌1小时，过滤少量甲醇冲洗，抽干得产品0.52公斤，精制收率89.7%，液相检测含量99.37%。
Claims (4)
1.一种N-苯基四氢-2-萘胺的制备方法，其特征在于，以N-苯基-2-萘胺为原料，氢气为还原剂，Raney Ni为催化剂，于高压釜中极性质子溶剂中加热条件下反应得到粗品，再经提纯后得到精品。
2.如权利要求1所述N-苯基四氢-2-萘胺的制备方法，其特征在于，所述极性质子溶剂为甲醇或乙醇。
3.如权利要求1所述N-苯基四氢-2-萘胺的制备方法，其特征在于，所述加热反应温度范围为：90℃～120℃。
4.如权利要求1所述N-苯基四氢-2-萘胺的制备方法，其特征在于，提纯溶剂优选甲醇，精制后经液相色谱检测质量含量大于99%。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011102505562A CN102351712B (zh) | 2011-08-29 | 2011-08-29 | N-苯基四氢-2-萘胺的制备方法 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011102505562A CN102351712B (zh) | 2011-08-29 | 2011-08-29 | N-苯基四氢-2-萘胺的制备方法 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102351712A CN102351712A (zh) | 2012-02-15 |
| CN102351712B true CN102351712B (zh) | 2013-11-27 |
Family
ID=45575386
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2011102505562A Active CN102351712B (zh) | 2011-08-29 | 2011-08-29 | N-苯基四氢-2-萘胺的制备方法 |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102351712B (zh) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2006807A1 (de) * | 1969-02-17 | 1971-07-22 | The Procter & Gamble Co , Cincm nati, Ohio (V St A ) | Schmiermittelgemische |
| US3943172A (en) * | 1972-10-06 | 1976-03-09 | A. Christiaens, Societe Anonyme | Derivatives of 2-amino-(1,2,3,4-tetrahydronaphthalene), the preparation and use thereof |
| WO2008011161A2 (en) * | 2006-07-21 | 2008-01-24 | Bridge Pharma, Inc. | Dermal anesthetic compounds |
-
2011
- 2011-08-29 CN CN2011102505562A patent/CN102351712B/zh active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2006807A1 (de) * | 1969-02-17 | 1971-07-22 | The Procter & Gamble Co , Cincm nati, Ohio (V St A ) | Schmiermittelgemische |
| US3943172A (en) * | 1972-10-06 | 1976-03-09 | A. Christiaens, Societe Anonyme | Derivatives of 2-amino-(1,2,3,4-tetrahydronaphthalene), the preparation and use thereof |
| WO2008011161A2 (en) * | 2006-07-21 | 2008-01-24 | Bridge Pharma, Inc. | Dermal anesthetic compounds |
Non-Patent Citations (2)
| Title |
|---|
| Baxter, Ellen W.等.Reductive aminations of carbonyl compounds with borohydride and borane reducing agents..《Organic Reactions (Hoboken, NJ, United States)》.2002,第59卷全文. |
| Reductive aminations of carbonyl compounds with borohydride and borane reducing agents.;Baxter, Ellen W.等;《Organic Reactions (Hoboken, NJ, United States)》;20021231;第59卷;全文 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102351712A (zh) | 2012-02-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| MX2007015420A (es) | Proceso para la sintesis de 5-(metil-ih-imidazol-1-il)-3-(trifluor ometil)-bencenamina. | |
| CN102351712B (zh) | N-苯基四氢-2-萘胺的制备方法 | |
| CN102241626A (zh) | 一种马来酸氟吡汀的合成工艺 | |
| CN101747284A (zh) | 一种抗氧剂的制备方法 | |
| CN105884746B (zh) | 氟马替尼的合成方法 | |
| CN110845415B (zh) | 一种环境友好的2-乙基-4-甲基咪唑合成方法 | |
| CN102432486A (zh) | 一种1,3-丙二醇-双(4-硝基苯甲酸)酯的合成方法 | |
| CN103073485B (zh) | 一种丁酸氯维地平的制备方法 | |
| CN108047258B (zh) | 一种合成氨基吡啶硼酸酯的方法 | |
| CN101735132B (zh) | N-甲基-2-羟乙基吡咯烷的合成方法 | |
| KR20210135238A (ko) | 중간체 화합물 2-클로로-5-메틸-4-피리딘아민을 사용한 2-클로로-5-메틸-4-니트로-피리딘-1-옥시드로부터의 4-아미노-5-메틸-1h-피리딘-2(1h)-온 (mr 길항제 피네레논의 합성을 위한 중간체 화합물)의 합성 | |
| CN101346352B (zh) | 不对称还原方法 | |
| CN107501159A (zh) | 维拉佐酮中间体3‑(4‑氯丁基)‑5‑氰基吲哚合成方法 | |
| CN106380439A (zh) | 一种水做溶剂钯炭还原法制备吲哚‑2‑甲酸 | |
| CN101168532B (zh) | 一种n-甲基哌嗪取代苯胺的合成方法 | |
| CN102442915A (zh) | 取代芳香烯胺类复杂化合物的制备方法 | |
| JPH04247069A (ja) | α位に塩素原子を有するアミノメチルピリジン類の製造方法 | |
| CN108689910B (zh) | 一种1-环己烯-1,2-二甲酰亚胺的合成方法 | |
| CN109836373B (zh) | 一种维生素b6的环保制备及尾气循环利用的方法 | |
| CN102993171B (zh) | 合成喹酞酮黄的方法 | |
| CN101531628A (zh) | 4-二甲胺基哌啶盐酸盐的合成方法 | |
| CN110002930B (zh) | 一种加氢还原烯基芳香卤代衍生物的方法 | |
| JPS63297363A (ja) | ３−メチルインド−ル類の製造法 | |
| CN101481320B (zh) | 一种4-氨基苯甲酸(4-氨基苯基)酯的制备方法 | |
| CN105439954A (zh) | 一种亚氨基芪的单步合成方法 |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C56 | Change in the name or address of the patentee | ||
| CP03 | Change of name, title or address |
Address after: 300384 Tianjin Xiqing Haitai green industry base K2-8-501 Patentee after: JUNKAI (TIANJIN) CHEMICAL CO., LTD. Address before: 300384 Tianjin city Nankai District New Technology Industrial Park Development Road No. 6 six Haitai Haitai green industry base K2 Building 8 Room 501 Patentee before: Junkai (Tianjin ) Chemical Co., Ltd. |
|
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20171013 Address after: Shijiazhuang City, Hebei Province West Bridge 050051 Lian Qi Road No. 2 Building 1 1 unit 502 Patentee after: Zhou Zujie Address before: 300384 Tianjin Xiqing Haitai green industry base K2-8-501 Patentee before: JUNKAI (TIANJIN) CHEMICAL CO., LTD. |
|
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20180912 Address after: 300384 Tianjin Xiqing District Hai Tai green industrial base K2-8-501 Patentee after: JUNKAI (TIANJIN) CHEMICAL CO., LTD. Address before: 050051 1 unit 1, No. 2, Lian Qi Road, Qiaoxi District, Shijiazhuang, Hebei, China. Patentee before: Zhou Zujie |
|
| CP01 | Change in the name or title of a patent holder | ||
| CP01 | Change in the name or title of a patent holder |
Address after: 300384 Tianjin Xiqing District Hai Tai green industrial base K2-8-501 Patentee after: Tianjin Junkai Agricultural Technology Co.,Ltd. Address before: 300384 Tianjin Xiqing District Hai Tai green industrial base K2-8-501 Patentee before: JUNKAI (TIANJIN) CHEMICAL Co.,Ltd. |