TW426668B - Process for the preparation of 3,5-lutidine and 3-picoline - Google Patents
Process for the preparation of 3,5-lutidine and 3-picoline Download PDFInfo
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- TW426668B TW426668B TW086115246A TW86115246A TW426668B TW 426668 B TW426668 B TW 426668B TW 086115246 A TW086115246 A TW 086115246A TW 86115246 A TW86115246 A TW 86115246A TW 426668 B TW426668 B TW 426668B
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- hydrogen
- oxide catalyst
- methyl
- pentanediamine
- inert gas
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- ITQTTZVARXURQS-UHFFFAOYSA-N 3-methylpyridine Chemical compound CC1=CC=CN=C1 ITQTTZVARXURQS-UHFFFAOYSA-N 0.000 title claims abstract description 70
- 238000000034 method Methods 0.000 title claims abstract description 54
- HWWYDZCSSYKIAD-UHFFFAOYSA-N 3,5-dimethylpyridine Chemical compound CC1=CN=CC(C)=C1 HWWYDZCSSYKIAD-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 46
- 239000001257 hydrogen Substances 0.000 claims abstract description 45
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 45
- 239000003054 catalyst Substances 0.000 claims abstract description 41
- 239000011261 inert gas Substances 0.000 claims abstract description 22
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 21
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 20
- JZUHIOJYCPIVLQ-UHFFFAOYSA-N 2-methylpentane-1,5-diamine Chemical compound NCC(C)CCCN JZUHIOJYCPIVLQ-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 19
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 19
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 19
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 19
- 229910052593 corundum Inorganic materials 0.000 claims abstract description 18
- 229910001845 yogo sapphire Inorganic materials 0.000 claims abstract description 18
- 239000012808 vapor phase Substances 0.000 claims abstract description 10
- 239000000203 mixture Substances 0.000 claims abstract description 9
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 8
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract 8
- 229910003158 γ-Al2O3 Inorganic materials 0.000 claims abstract 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 26
- OISVCGZHLKNMSJ-UHFFFAOYSA-N 2,6-Lutidine Substances CC1=CC=CC(C)=N1 OISVCGZHLKNMSJ-UHFFFAOYSA-N 0.000 claims description 16
- 239000000047 product Substances 0.000 claims description 16
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 239000007789 gas Substances 0.000 claims description 13
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 8
- 238000004821 distillation Methods 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 6
- DFPAKSUCGFBDDF-UHFFFAOYSA-N nicotinic acid amide Natural products NC(=O)C1=CC=CN=C1 DFPAKSUCGFBDDF-UHFFFAOYSA-N 0.000 claims description 6
- 239000012263 liquid product Substances 0.000 claims description 5
- 229910021529 ammonia Inorganic materials 0.000 claims description 4
- 230000002079 cooperative effect Effects 0.000 claims description 4
- 238000005984 hydrogenation reaction Methods 0.000 claims description 4
- 239000000543 intermediate Substances 0.000 claims description 4
- 235000005152 nicotinamide Nutrition 0.000 claims description 4
- 239000011570 nicotinamide Substances 0.000 claims description 4
- KJOMYNHMBRNCNY-UHFFFAOYSA-N pentane-1,1-diamine Chemical compound CCCCC(N)N KJOMYNHMBRNCNY-UHFFFAOYSA-N 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 claims description 2
- 239000004593 Epoxy Substances 0.000 claims description 2
- PVNIIMVLHYAWGP-UHFFFAOYSA-N Niacin Chemical compound OC(=O)C1=CC=CN=C1 PVNIIMVLHYAWGP-UHFFFAOYSA-N 0.000 claims description 2
- 239000003905 agrochemical Substances 0.000 claims description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims description 2
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 claims description 2
- 150000001728 carbonyl compounds Chemical class 0.000 claims description 2
- 238000005260 corrosion Methods 0.000 claims description 2
- 230000007797 corrosion Effects 0.000 claims description 2
- 238000004132 cross linking Methods 0.000 claims description 2
- 239000003814 drug Substances 0.000 claims description 2
- 238000005516 engineering process Methods 0.000 claims description 2
- CBOIHMRHGLHBPB-UHFFFAOYSA-N hydroxymethyl Chemical compound O[CH2] CBOIHMRHGLHBPB-UHFFFAOYSA-N 0.000 claims description 2
- 239000003112 inhibitor Substances 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 229960003966 nicotinamide Drugs 0.000 claims description 2
- 229960003512 nicotinic acid Drugs 0.000 claims description 2
- 239000012071 phase Substances 0.000 claims description 2
- 239000010970 precious metal Substances 0.000 claims description 2
- 150000003222 pyridines Chemical class 0.000 claims description 2
- IAHFWCOBPZCAEA-UHFFFAOYSA-N succinonitrile Chemical compound N#CCCC#N IAHFWCOBPZCAEA-UHFFFAOYSA-N 0.000 claims description 2
- 230000002194 synthesizing effect Effects 0.000 claims description 2
- HPYNZHMRTTWQTB-UHFFFAOYSA-N 2,3-dimethylpyridine Chemical compound CC1=CC=CN=C1C HPYNZHMRTTWQTB-UHFFFAOYSA-N 0.000 claims 4
- VHRGRCVQAFMJIZ-UHFFFAOYSA-N cadaverine Chemical compound NCCCCCN VHRGRCVQAFMJIZ-UHFFFAOYSA-N 0.000 claims 2
- 238000002156 mixing Methods 0.000 claims 2
- 229910052704 radon Inorganic materials 0.000 claims 2
- SYUHGPGVQRZVTB-UHFFFAOYSA-N radon atom Chemical compound [Rn] SYUHGPGVQRZVTB-UHFFFAOYSA-N 0.000 claims 2
- 230000009469 supplementation Effects 0.000 claims 2
- 102100040412 Amyloid beta A4 precursor protein-binding family B member 1-interacting protein Human genes 0.000 claims 1
- 101000964223 Homo sapiens Amyloid beta A4 precursor protein-binding family B member 1-interacting protein Proteins 0.000 claims 1
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 claims 1
- 230000007123 defense Effects 0.000 claims 1
- 201000010099 disease Diseases 0.000 claims 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 claims 1
- 244000005700 microbiome Species 0.000 claims 1
- 239000000377 silicon dioxide Substances 0.000 abstract 2
- 235000012239 silicon dioxide Nutrition 0.000 abstract 2
- 238000010924 continuous production Methods 0.000 description 3
- 239000012530 fluid Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- -1 2-fluorenyl Chemical group 0.000 description 1
- QVRSLPLQNXZLII-UHFFFAOYSA-N 3,5-dipyridin-2-ylpyridine Chemical compound N1=CC=CC=C1C1=CN=CC(C=2N=CC=CC=2)=C1 QVRSLPLQNXZLII-UHFFFAOYSA-N 0.000 description 1
- 241000272165 Charadriidae Species 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 238000005485 electric heating Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000003701 inert diluent Substances 0.000 description 1
- 229910052743 krypton Inorganic materials 0.000 description 1
- DNNSSWSSYDEUBZ-UHFFFAOYSA-N krypton atom Chemical compound [Kr] DNNSSWSSYDEUBZ-UHFFFAOYSA-N 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 235000015170 shellfish Nutrition 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000003325 tomography Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/06—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom
- C07D213/08—Preparation by ring-closure
- C07D213/09—Preparation by ring-closure involving the use of ammonia, amines, amine salts, or nitriles
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/06—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom
- C07D213/08—Preparation by ring-closure
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Pyridine Compounds (AREA)
Description
426668. 第86115246號專利申請專利 中文説明書修正頁(88年1月)五、發明説明() 1
經濟部中央標準局員工消費合作·杜印t 發明領域 本發明爲一種製備3,5-二甲基吡啶和3_甲基吡啶之方 法。 發明背景 —曱基吡哫(3,5-丨utidine,也稱爲 3;5_dimethylpyridine) 係被用冑環氧交聯反應中的觸媒,於高溫應用中作爲溶 劑,及在醫藥,農化品和腐蝕抑制劑中作爲中間體。 3-甲基吡啶(3-picoline,也稱爲3_methylpyridine)係在菸鹼 酸和菸鹼醯胺的製造中作爲中間體。其也可用爲溶劑。 Re iff等人(U_ S. 3,80 3.,152)提及一種用戊二酸或丁二酸二 腈與氫在貴重金屬氫化觸媒上行氣相反應以製備吡啶或吡 11各之方法。 ▽以1^心11&11(1〇1^(1;.3.4,189,585)提及一種用2-甲基 晚啶於金屬氫化觸媒上在25〇-3 6 0°C行去曱基化反應製備吡 啶和2,6 -二甲基吡啶之方法。 有許多專利提及有關用羰基化合物和氨反應製備吡啶和 經烷基取代吡啶之技術。例如,可參看U. S · 5,Ο 1 3,8 4 3, U. S. 4,481,361,U. S. 4,429,131 和U. S. 4,220,7 83。 Braden and Dieterich(U. S. 3,689,496)提及用二曱醇基 烷,R-C(CH2OH)3,與氨或胺反應製備烷基吡啶。 發明概述 本發明爲一種用2 -甲基-1,5 -戊烷二胺與氫在約400-5 00 下於氧化物觸媒上行蒸氣相反應以合成3,5 -二甲基吡啶 -4 - 本紙法尺度適用中國國家標準(CNS ) A4規格(210X297公釐) (請先閲讀背面之注意事項再填寫本頁) 訂 線. 經濟部中央標準局具工消費合作社印裝 ^26668 、發明説明(: <方法。3 -甲基吡啶也可以用本發明方法反應製得。這些 所得產物可經由蒸餾或其他適當手段冷凝分離出。 一 本發明方法較佳者係以產生產物流之連續程序進行,其 包括下列步驟:(a)將氫氣或混合著惰性氣體的氫氣與揮發 出的2 -甲基_1,5_戊烷二胺給過於4〇〇_5〇〇χ:下的氧化物觸 媒之上;(b)從產物流冷凝出液態產物,,及(c)回收3,5_二 甲基吡啶和3 -甲基吡啶。 較佳者爲使用蒸餾法來分離和回收3,5 -二甲基吡啶與3 _ 甲基p比咬產物。 登明之詳細説明 本發明係有關一種合成3,5-二甲基吡啶之方法,其包括 用2 -甲基·ι,5_戊燒二胺和氫氣在氧化物觸媒上於約4〇〇_ 500°C下行蒸氣相反應。 與3,5 -二甲基吡啶_起地,也產生3_甲基吡啶。這些所 得產物可經蒸餾或其他適當手段予以冷凝和分離出。本發 明方法所得3,5 -二甲基吡啶的產率爲排出產物流的丨〇_25重 量% ’其餘典型地爲3 -甲基吡啶及/或未反應的2 _甲基_ 1,5-戊二胺。 雖然本發明方法可爲批式或連續式程序,不過較佳者爲 以連續式程序實施本發明方法。需要提供熱量給反應且可 以用能達到反應溫度的任何適當手段來供给。適當的反應 溫度範圍爲35(TC至550°C »較佳的溫度範圍爲4〇〇_5〇〇。〇。 適當的氧化物觸媒包括Al2〇3,Si〇2,gamma-Al203, gamma-Ai2〇3/Si02, Ti02, Zr024彼等的混合物。較佳者爲 -5 本紙張尺度適用中囤國家標準(CNS ) A(4規格(21〇χ297公釐 (請先閲讀背面之注意事項再填寫本頁)
426668 A7
Al2〇3 或 A1203/Si02,。最佳者爲 gamma.Al2〇3,或 A12〇3/Si〇2 ο Al2〇3或Si〇2在各種混合氧化物中的重量比例 可爲在氧化物觸媒中的9/1至1/9,而不會對本發明方法有 實質的影響。 ' 於連續程序中,本發明方法可以用混合床或流體床程序 來進行。氧化物觸媒的粒度,粒子形狀或本質都經選擇得 適用於合床或流體床程序者β對於流體床操作通常需要小 的抗磨損粉末及/或粒子〇混合床程序典型地係使用丸/ 球,或擠壓物,其尺寸通常是在1/16至1/4吋直徑範圍之 内。 氫氣或混合著惰性氣體的氳氣,或彼等的混合物可與蒸 發出的有機進料共給入。惰性氣體包括不會與反應物反應 或在本發明方法的溫度條件下不會反應之氣體,例如,氮 氣,氦氣或氬氣。惰性氣體係用來提供稀釋者。本、發明方 法需要有最少四莫耳的氫氣對一莫耳的2_甲基·15-戊二 胺。本發明方法中,氣體進料總莫耳數(氫氣莫耳數加上惰 性稀釋氣體莫耳數)對2 -甲基-1,5 -戊二胺莫耳數的比例可 爲5/1至40/1。較佳的莫耳比例爲2〇/1至3〇/1。本發明方法的 經濟部中央標準局貝工消費合作社印裝 装! (請先聞讀背面之注意事項再填寫本頁) 、1Τ 反應壓力可爲從稍高於大氣壓至稍低於大氣壓,而以大氣 壓較爲佳。 .實施例 通則 實施例中所用反應器爲U -形玻璃反應器,其具有一較大 直徑的支管,其内裝著玻璃珠粒而作爲蒸發段所用。其較 ___-6- 本紙張ΛΜ用中闕家痴!( CNS ) Α4· ( 2歌297公楚) ~ 一 經濟部中央標準局員工消费合作社印装
A 2 6 6 6 B A7 --------------- - B7 五、發明説明(4 ) ' 小直徑的第二支管裝著觸媒床。各反應器支管皆約柳毫米 長;較大支管的内徑爲19毫米;較小支管的内徑爲1〇毫 米。 整個反應器單元都放置在_電熱砂浴内,其溫度係經熱 電偶及電子溫度控制器所控制者。液體和氣體兩種進料都 是對蒸發器段的頂端加入(向下流)且然後流經觸媒床(向上 流),再冷凝,收集,和分析。 氣體流量以標準立方厘米每單位時間表出並由Br〇〇ks氣 •體流速計予以控制。液體流係經ISC0計量泵予以控制和計 量。 產物流的分析係用30米dB 1701 me3ab〇re管柱以氣體層 析術完成的。分析所用的溫度程式如下:9〇〇c,以6度/分 增溫到200 C ;將溫度保持在2〇〇°c 1〇分鐘。注射器溫度爲 200 C 彳貞檢器溫度爲250 C。分析產物流所含的3,5 -二曱 基吡啶(LUT) ’未經反應的2 -曱基·ι,5·戊二胺(MPMD), 3 -甲基吡啶(3PIC),及,恰當者,微量的雜質(用質譜術鑑 定未知物)。下面表中所列値係以面積百分比表出。 實施例1 此實施例闡述gamma-Α12〇3觸媒之使用。將6.11克99%呈 1/8吋鍵形式的 gamma-Al203( Johnson Matthey觸媒,Catalog # 1286,Lot No. D17A03)在400°G下用80立方厘米/分的氫 氣流處理一小時。於反應期間使用3 0立厘米/分的氫氣流 及0.3立方厘米/小時的MPMD流。在操作2小時後將溫度從 400提升到450°C且於操作5小時後提升到500eC。其結果表 本紙涑尺度適用中國國家標準(CNS > A4規格(2丨0X297公釐) (請先閱讀背面之注意事項再填寫本頁) -裝· 訂 26668^ A7 B7 五、發明説明(5 ) 於表1之中。 Jj_ 時間,小時 溫度,。c LUT, % 3PIC, % 1.0 400 16.4 69.9 2.0 400 18.7 55.8 3.0 450 12.7 61.9 4.0 450 15.8 67.4 5.0 450 15.3 66.0 • 6.0 500 13.5 70.6 7.0 500 13.1 70.7 實施例2 I.JiJ------i-- * } (請先閲讀背面之注$項再填寫本頁) 訂 此實施例闡示第二種形式的氧化物觸媒。將6.01克,1/8 吋擠壓物形式的 0amma-AU〇3(Engelhard Al-4198, Lot No 583A-22-33-41)置於反應器管内並以80立方厘米/分的氫氣 在400°C下處理1小時予以活化。 反應物流係以3 〇立方厘米/分的氫氣流和〇. 3立方厘米/小 時的MPMD流通過觸媒。反應器的溫度係在操作4小時後從 400°C提升到45〇°C並續保持1 4小時。 表2中將反應產物,3,5 -二甲基吡啶(LUT)和3 -甲基吡 啶,的重量百分比相對於反應溫-度列出。 表2 時間,小時 溫度,°C LUT, % 3PIC, % -8 - 本紙張尺度適用中關家揉準(CNS ) A4規格(21GX297公釐) i 經濟部中央梂準局員工消費合作社印装 d266 6 8 , A7 B7 五、發明説明(6 ) 1.0 400 18.6 25.1 2.0 400 15.5 22.1 4.0 400 12.2 24.1 5.5 450 21.6 37.6 6.0 450 23.6 43.8 8.0 450 23.5 50.8 10.0 450 23.5 44.5 12.0 450 22.1 48.2 14.0 450 20.0 50.8 16.0 450 21.8 50.1 18.0 450 22.0 47.4 I一 "T·;~~: ^裝---, > (請先閔讀背面之注意事項再填寫本頁)
.1T 經濟部中央標準局員工消費合作社印製 -9- 本紙乐尺度適用中國國家標隼(CNS ) A4規格(210X297公釐)
Claims (5)
- 4266 6 8 | 第861 i524㈣專利申請專利 發 中文申請專利範圍修正本(89年4月)品 '二甲基吡啶和3 -甲基吡啶之方法,其包括 在蒸氣相中用2 -甲基-1,5 -戊二胺與氫氣或混合著惰性氣 體的氣氣於氧化物觸媒上於400至500°C之溫度下反應, 及回收3,5 -二甲基吡啶與3 -甲基吡啶,其中氫氣或混 合著惰性氣體的氫氣相對於2 -甲基-1,5 -戊二胺之莫耳濃 度的莫耳比為5/1至40/1且該氧化物觸媒係選自下列所 成組合之中者:八1203,8102,呂311111^-入1203,§&11111^-Al203/Si02, Ti02, Zr02或彼等的混合物。, 2_如申請專利範圍第1項之方法,其中該方法係連續式者且 產一產物流,該方法包括下列諸步驟:(a)將氳氣或混合 著惰性氣體的氫氣與蒸發出的2 -甲基-1,5-戊二胺給過處 於400-500°C下的氧化物觸媒;(b)從產物流冷凝出液態 產物,及(c)回收3 ,5 -二甲基吡啶和3 -甲基吡啶。 3. 如申請專利範圍第2項之方法’其中係使用蒸餾操作來分 離和回收3,5-二甲基吡啶與3-甲基吡淀。 4. 如申請專利範圍第3項之方法’其中該氧化物觸媒為 gamma-Al2〇3 4gamma-Al2〇3/Si〇2。/ ^^^1 - l·· — I....... —^ϋ nn I t n (请先閲讀背面之注意事項再填寫本頁) 訂 經濟部中央揉準局負工消费合作社印«. 本紙張尺度逍用中國國家標準(CNS ) A4規格(210X297公釐) •-5» CJ 修正補充 举 a a 公告衣 第86115246號專利ψ請案 英文申請專利範圍修正本(89年4月) ROC (Taiwan) Patent Application No. 86115246 _ Amended Claims ("Anril 2000">_ 1, A process for the preparation of 3f5-lutidine and 3-picoline which comprises reacting in vapor phase 2-methyl-1,5-pentanediamine and hydrogen or hydrogen mixed with an inert gas over an oxide catalyst at temperatures from 400 to 500°C and recovering 3*5-lutidine and 3-picoline, wherein the hydrogen or hydrogen mixed with the inert gas is present in a molar ratio from 5/1 to 40/1 compared to the molar concentration of 2-methyl-1,5-pentanediamine and the oxide catalyst is selected from the group consisting of Al2〇3, Si〇2, gamma-Al2〇3r gamma-AI2O3/Si〇2/ Ti02/ Zr02 or mixture thereof.
- 2, The process according to Claim 1 wherein the process is continuous and produces a product stream comprising the steps: (a) feeding hydrogen or hydrogen mixed with inert gases and volatilized 2-methyl-X^5-pentanediamine over an oxide catalyst at about 400-500oC, (b) condensing liquid products from the product stream, and (c) recovering 3,5-lutidine and 3-picoline.
- 3. The process of Claim 2 where distillation is used to separate and recover 3f5-lutidine and 3-picoline.
- 4. The process of Claim 3 where the oxide catalyst is gamma"Al2〇3 or gamma-Al2〇3/Si02. U.\PTSNCTVNW«6115246.DOC \ 經濟部中央標準局貞工消費合作社印策 4266 6 8 ^ 申請案號861ί524<附 送書件 十十九八七六五四三二一 (由本局填寫) (請先κ讀背面之注意1f項再本瓦各棚) 申請日期86. 10.16 案由:10000 規費 新台伍佰元整 聲明事項 □本案係符合專利法第二+條第一项□第一款但書或□第 三款但書規定之期間,其日期爲 年 月 曰〇 □本案係有闞微生物。 □主張優先椎: 受理該申請案之國家(地區): 申請日: 申請案號數:.人 理代 # 專 電話 事務所 D 姓名 、、文微本主―一一宜圖説 牟件生案張説委發誓式明 利,物肴優明任明書一書 法正寄Μ先書牟人一式一 施本存8權原利與份二式 行及機防之本代申。份二 細影構機證係理請 則本之密明外人人 S1 第各寄诳文8代非 十乙存明件文爲同 ^ 三份正者申一 條。明件本人 規文正及原者v 定件本影文'-申 之或乙本説代請 證易份各明理權 .明於。乙書委證 文被份一任明 件得。式書書 之 二- 證 明 份份份 請審查並准予「 3,5-二甲基呲啶之製備 PSPARATION OF 3,5-LUTIDINE 發明專利 經擠部中央標準局 發明專利申請 發 明 人 中 請 人 住 '居所 D 名 姓 英文 中文 代表人 住 '居所 {事務所) D 稱 名 或 名 姓 書 英文 宁又 七一五三三〇〇 台北市敦化北路二〇一號七樓 00743645 陳長文律師 a 备章 美國德來懷州威明頓市烏瓦德路一7號;: RONALD LEE AMEY 7-' 羅那德里亞米 等/人) 馬瑞安,迪.麥克奈海 §RIAM D. MECONNAHEY 簽章 美國德來懷州威明頓市馬卡第街1007號 (本地址與r向责局申請者□相同□不同) COO0I E. I. DU PONT DEMEMOURS AND OOMPANY 美商杜邦股份有限公司 簽幸 □指定「$又送達人」(見背面说明)(等/人) 台7R字 第J號 專利代 理人證 書字號 美國 國籍 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐> 電話 美國 國籍 (八六)理專程三一八字第一671¾ 中華民國/ _ 7- 6· 8 ¾檄t收德000 公告衣 申請EJ期 --86.ΐη,ΐ(ί 案 號 類 別 i JL —__— (以上各糊由本局填註)426668 中文説明書修i頁(88年1月) C4 ^請委員明示,本炱修正後^^|!史原^質_釔 經濟部中央操隼局負工消費合作社印製 11 專利説明書 -:名稱 中文 3,5-二甲基P比症和3-甲基砟(:症之製法 新型 ^ 英文 PROCESS FOR THE PREPARATION OF 3,5-LUTIDINE AND 3-PICOLINE 姓 名 羅那德里亞米 二、發明人 創作 國 藉 美國 住 '居所 美國德來懷州威明頓市烏瓦德路17號 姓 名 (名稱) 美商杜邦股份有限公司 國 藉 美國 三、申請人 住、居所 (事務所) 美國德來懷州威明頓市馬卡第街1007號 代表人 姓 名 馬瑞安·迪麥克奈海 . -1 ..... 訂 裝 426668. 第86115246號專利申請專利 中文説明書修正頁(88年1月)五、發明説明() 1經濟部中央標準局員工消費合作·杜印t 發明領域 本發明爲一種製備3,5-二甲基吡啶和3_甲基吡啶之方 法。 發明背景 —曱基吡哫(3,5-丨utidine,也稱爲 3;5_dimethylpyridine) 係被用冑環氧交聯反應中的觸媒,於高溫應用中作爲溶 劑,及在醫藥,農化品和腐蝕抑制劑中作爲中間體。 3-甲基吡啶(3-picoline,也稱爲3_methylpyridine)係在菸鹼 酸和菸鹼醯胺的製造中作爲中間體。其也可用爲溶劑。 Re iff等人(U_ S. 3,80 3.,152)提及一種用戊二酸或丁二酸二 腈與氫在貴重金屬氫化觸媒上行氣相反應以製備吡啶或吡 11各之方法。 ▽以1^心11&11(1〇1^(1;.3.4,189,585)提及一種用2-甲基 晚啶於金屬氫化觸媒上在25〇-3 6 0°C行去曱基化反應製備吡 啶和2,6 -二甲基吡啶之方法。 有許多專利提及有關用羰基化合物和氨反應製備吡啶和 經烷基取代吡啶之技術。例如,可參看U. S · 5,Ο 1 3,8 4 3, U. S. 4,481,361,U. S. 4,429,131 和U. S. 4,220,7 83。 Braden and Dieterich(U. S. 3,689,496)提及用二曱醇基 烷,R-C(CH2OH)3,與氨或胺反應製備烷基吡啶。 發明概述 本發明爲一種用2 -甲基-1,5 -戊烷二胺與氫在約400-5 00 下於氧化物觸媒上行蒸氣相反應以合成3,5 -二甲基吡啶 -4 - 本紙法尺度適用中國國家標準(CNS ) A4規格(210X297公釐) (請先閲讀背面之注意事項再填寫本頁) 訂 線.申請專利 中文説明書修正頁(88年1月) A5 ______ 四、中文發明摘要(發明之名稱:3,5-二甲基吡啶和3_甲基吡啶之製法 (請先聞讀背面之注意事項再填寫本頁各糊} 一種製備3,5 -二甲基吡啶和3 _甲基吡啶之方法,其包括 在蒸氣相中用2 -甲基-1,5 -戊二胺與氫氣或混合著惰性氣體 的氫氣於氧化物觸媒上於4〇〇至5〇〇°C之溫度下反應,其中 氫氣或混合著惰性氣體的氫氣相對於z _曱基_丨,5 -戊二胺之 莫耳濃度的莫耳比爲5 /1至4 0 /1且其中該氧化物觸媒係選自 下列所成組合之中者:八1:2〇3,8丨〇2,旦&1]11113-八12〇3,§31111113-Al2〇3/Si〇2,Ti〇2,Zr〇2或彼等的混合物。 英文發明摘要(發明之名稱PROCESS FOR THE PREPARATION OF 3,5- LUTIDINE AND 3-PICOLINE 經濟部中央標準局員工消費合作社印策 The present invention is a process for the preparation of 3,5-Iutidine and 3-picoline which comprises reacting in vapor phase 2-methyl-1, 5~ pentanediamine and hydrogen or hydrogen mixed with an inert gas over an oxide catalyst at temperatures from 400 to_ 500°c wherein the hydrogen or hydrogen mixed with the inert gas is prsssnii in s. γλο 1 ar ratio from 5/1 to 40/1 compared to the molar concentration of 2-methyl-1,5-pentanediamine and the oxide catalyst is selected from the group consisning or AI-O3, Si〇2, gamma-Al2〇3, gamma-AI^O./SiO:, TiO:/ Zr02 or mixture thereof. 本紙張尺度適用中國國家標準(CNS ) A4规格(210X 297公釐) 4266 6 8 | 第861 i524㈣專利申請專利 發 中文申請專利範圍修正本(89年4月)品 '二甲基吡啶和3 -甲基吡啶之方法,其包括 在蒸氣相中用2 -甲基-1,5 -戊二胺與氫氣或混合著惰性氣 體的氣氣於氧化物觸媒上於400至500°C之溫度下反應, 及回收3,5 -二甲基吡啶與3 -甲基吡啶,其中氫氣或混 合著惰性氣體的氫氣相對於2 -甲基-1,5 -戊二胺之莫耳濃 度的莫耳比為5/1至40/1且該氧化物觸媒係選自下列所 成組合之中者:八1203,8102,呂311111^-入1203,§&11111^-Al203/Si02, Ti02, Zr02或彼等的混合物。, 2_如申請專利範圍第1項之方法,其中該方法係連續式者且 產一產物流,該方法包括下列諸步驟:(a)將氳氣或混合 著惰性氣體的氫氣與蒸發出的2 -甲基-1,5-戊二胺給過處 於400-500°C下的氧化物觸媒;(b)從產物流冷凝出液態 產物,及(c)回收3 ,5 -二甲基吡啶和3 -甲基吡啶。 3. 如申請專利範圍第2項之方法’其中係使用蒸餾操作來分 離和回收3,5-二甲基吡啶與3-甲基吡淀。 4. 如申請專利範圍第3項之方法’其中該氧化物觸媒為 gamma-Al2〇3 4gamma-Al2〇3/Si〇2。/ ^^^1 - l·· — I....... —^ϋ nn I t n (请先閲讀背面之注意事項再填寫本頁) 訂 經濟部中央揉準局負工消费合作社印«. 本紙張尺度逍用中國國家標準(CNS ) A4規格(210X297公釐) •-5» CJ 修正補充 举 a a 公告衣 第86115246號專利ψ請案 英文申請專利範圍修正本(89年4月) ROC (Taiwan) Patent Application No. 86115246 _ Amended Claims ("Anril 2000">_ 1, A process for the preparation of 3f5-lutidine and 3-picoline which comprises reacting in vapor phase 2-methyl-1,5-pentanediamine and hydrogen or hydrogen mixed with an inert gas over an oxide catalyst at temperatures from 400 to 500°C and recovering 3*5-lutidine and 3-picoline, wherein the hydrogen or hydrogen mixed with the inert gas is present in a molar ratio from 5/1 to 40/1 compared to the molar concentration of 2-methyl-1,5-pentanediamine and the oxide catalyst is selected from the group consisting of Al2〇3, Si〇2, gamma-Al2〇3r gamma-AI2O3/Si〇2/ Ti02/ Zr02 or mixture thereof. 2, The process according to Claim 1 wherein the process is continuous and produces a product stream comprising the steps: (a) feeding hydrogen or hydrogen mixed with inert gases and volatilized 2-methyl-X^5-pentanediamine over an oxide catalyst at about 400-500oC, (b) condensing liquid products from the product stream, and (c) recovering 3,5-lutidine and 3-picoline. 3. The process of Claim 2 where distillation is used to separate and recover 3f5-lutidine and 3-picoline.
- 4. The process of Claim 3 where the oxide catalyst is gamma"Al2〇3 or gamma-Al2〇3/Si02. U.\PTSNCTVNW«6115246.DOC \
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US08/725,434 US5708176A (en) | 1996-10-03 | 1996-10-03 | Preparation of 3,5-lutidene |
Publications (1)
Publication Number | Publication Date |
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TW426668B true TW426668B (en) | 2001-03-21 |
Family
ID=24914539
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
TW086115246A TW426668B (en) | 1996-10-03 | 1997-10-16 | Process for the preparation of 3,5-lutidine and 3-picoline |
Country Status (9)
Country | Link |
---|---|
US (1) | US5708176A (zh) |
EP (1) | EP0929523B1 (zh) |
JP (1) | JP2001501623A (zh) |
KR (1) | KR100474624B1 (zh) |
CA (1) | CA2263912A1 (zh) |
DE (1) | DE69705849T2 (zh) |
EA (1) | EA001774B1 (zh) |
TW (1) | TW426668B (zh) |
WO (1) | WO1998014428A1 (zh) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103044317A (zh) * | 2013-01-07 | 2013-04-17 | 清华大学 | 制备3-甲基吡啶的方法和系统 |
CN103301823A (zh) * | 2012-03-15 | 2013-09-18 | 清华大学 | 催化剂及其用途 |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2010034616A1 (en) * | 2008-09-26 | 2010-04-01 | Dsm Ip Assets B.V. | Method for the preparation of 3-methylpyridine |
RU2474473C1 (ru) * | 2011-09-16 | 2013-02-10 | Российская Федерация, От Имени Которой Выступает Министерство Промышленности И Торговли Российской Федерации | КАТАЛИЗАТОР, СПОСОБ ЕГО ПРИГОТОВЛЕНИЯ И СПОСОБ ПОЛУЧЕНИЯ β-ПИКОЛИНА |
CN104492479B (zh) * | 2014-12-10 | 2017-01-11 | 中国科学院大连化学物理研究所 | 一种3-甲基吡啶制吡啶催化剂及其制备方法 |
Family Cites Families (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE1795239B2 (de) * | 1968-08-27 | 1978-04-20 | Bayer Ag, 5090 Leverkusen | Verfahren zur Herstellung von symmetrischen 3,5-Dialkylpyridinen |
DE2045880A1 (de) * | 1970-09-17 | 1972-03-23 | Farbenfabriken Bayer Ag, 5090 Leverkusen | Verfahren zur Herstellung von 3,5-Dimethylpyridin |
US4189585A (en) * | 1970-12-04 | 1980-02-19 | Stamicarbon, B.V. | Process for the preparation of pyridine and 2,6-lutidine |
DE3104765A1 (de) * | 1981-02-11 | 1982-09-02 | Basf Ag, 6700 Ludwigshafen | Verfahren zur herstellung von pyridinen oder pyrrolen aus (alpha),(omega)-dinitrilen |
CH656879A5 (de) * | 1981-07-09 | 1986-07-31 | Lonza Ag | Verfahren zur herstellung von 3,5-dialkylpyridinen. |
US5149816A (en) * | 1988-07-11 | 1992-09-22 | Reilly Industries | High temperature process for selective production of 3-methylpyridine |
-
1996
- 1996-10-03 US US08/725,434 patent/US5708176A/en not_active Expired - Fee Related
-
1997
- 1997-10-03 WO PCT/US1997/017730 patent/WO1998014428A1/en active IP Right Grant
- 1997-10-03 EA EA199900353A patent/EA001774B1/ru not_active IP Right Cessation
- 1997-10-03 CA CA002263912A patent/CA2263912A1/en not_active Abandoned
- 1997-10-03 EP EP97909923A patent/EP0929523B1/en not_active Expired - Lifetime
- 1997-10-03 DE DE69705849T patent/DE69705849T2/de not_active Expired - Fee Related
- 1997-10-03 JP JP10516849A patent/JP2001501623A/ja not_active Withdrawn
- 1997-10-03 KR KR10-1999-7002852A patent/KR100474624B1/ko not_active IP Right Cessation
- 1997-10-16 TW TW086115246A patent/TW426668B/zh not_active IP Right Cessation
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103301823A (zh) * | 2012-03-15 | 2013-09-18 | 清华大学 | 催化剂及其用途 |
CN103044317A (zh) * | 2013-01-07 | 2013-04-17 | 清华大学 | 制备3-甲基吡啶的方法和系统 |
CN103804284A (zh) * | 2013-01-07 | 2014-05-21 | 清华大学 | 用于制备3-甲基吡啶的系统 |
CN103044317B (zh) * | 2013-01-07 | 2015-07-29 | 清华大学 | 制备3-甲基吡啶的方法和系统 |
CN103804284B (zh) * | 2013-01-07 | 2015-12-02 | 清华大学 | 用于制备3-甲基吡啶的系统 |
Also Published As
Publication number | Publication date |
---|---|
JP2001501623A (ja) | 2001-02-06 |
US5708176A (en) | 1998-01-13 |
KR20000048850A (ko) | 2000-07-25 |
DE69705849T2 (de) | 2002-04-04 |
DE69705849D1 (de) | 2001-08-30 |
CA2263912A1 (en) | 1998-04-09 |
EP0929523A1 (en) | 1999-07-21 |
EA001774B1 (ru) | 2001-08-27 |
EA199900353A1 (ru) | 1999-08-26 |
EP0929523B1 (en) | 2001-07-25 |
KR100474624B1 (ko) | 2005-03-08 |
WO1998014428A1 (en) | 1998-04-09 |
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