CN1169759C - 取代芳香化合物的制备方法 - Google Patents
取代芳香化合物的制备方法 Download PDFInfo
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- CN1169759C CN1169759C CNB018012299A CN01801229A CN1169759C CN 1169759 C CN1169759 C CN 1169759C CN B018012299 A CNB018012299 A CN B018012299A CN 01801229 A CN01801229 A CN 01801229A CN 1169759 C CN1169759 C CN 1169759C
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- 125000005843 halogen group Chemical group 0.000 claims abstract description 19
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- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 4
- 239000001257 hydrogen Substances 0.000 claims abstract description 4
- 125000000962 organic group Chemical group 0.000 claims abstract description 3
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- 238000006243 chemical reaction Methods 0.000 claims description 64
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 13
- 150000002500 ions Chemical class 0.000 claims description 13
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- 125000001183 hydrocarbyl group Chemical group 0.000 abstract 1
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- 239000002904 solvent Substances 0.000 description 10
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- 238000006467 substitution reaction Methods 0.000 description 8
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- 238000010534 nucleophilic substitution reaction Methods 0.000 description 7
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 6
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- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- NZNMSOFKMUBTKW-UHFFFAOYSA-N cyclohexanecarboxylic acid Chemical compound OC(=O)C1CCCCC1 NZNMSOFKMUBTKW-UHFFFAOYSA-N 0.000 description 6
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- LPNBBFKOUUSUDB-UHFFFAOYSA-N p-toluic acid Chemical compound CC1=CC=C(C(O)=O)C=C1 LPNBBFKOUUSUDB-UHFFFAOYSA-N 0.000 description 6
- 238000004445 quantitative analysis Methods 0.000 description 6
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- 150000001412 amines Chemical class 0.000 description 5
- 125000001246 bromo group Chemical group Br* 0.000 description 5
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- 125000001153 fluoro group Chemical group F* 0.000 description 5
- 230000035484 reaction time Effects 0.000 description 5
- NIBFJPXGNVPNHK-UHFFFAOYSA-N 2,2-difluoro-1,3-benzodioxole-4-carbaldehyde Chemical group C1=CC(C=O)=C2OC(F)(F)OC2=C1 NIBFJPXGNVPNHK-UHFFFAOYSA-N 0.000 description 4
- MSXVEPNJUHWQHW-UHFFFAOYSA-N 2-methylbutan-2-ol Chemical compound CCC(C)(C)O MSXVEPNJUHWQHW-UHFFFAOYSA-N 0.000 description 4
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- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 4
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- 150000002828 nitro derivatives Chemical class 0.000 description 1
- MCSAJNNLRCFZED-UHFFFAOYSA-N nitroethane Chemical compound CC[N+]([O-])=O MCSAJNNLRCFZED-UHFFFAOYSA-N 0.000 description 1
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- 125000002524 organometallic group Chemical group 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
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- 229940059574 pentaerithrityl Drugs 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- IDISMEQKBNKWJX-UHFFFAOYSA-N phenol;pyridine Chemical class C1=CC=NC=C1.OC1=CC=CC=C1 IDISMEQKBNKWJX-UHFFFAOYSA-N 0.000 description 1
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- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 description 1
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- 238000000926 separation method Methods 0.000 description 1
- NESLWCLHZZISNB-UHFFFAOYSA-M sodium phenolate Chemical compound [Na+].[O-]C1=CC=CC=C1 NESLWCLHZZISNB-UHFFFAOYSA-M 0.000 description 1
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- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
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- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- IAHFWCOBPZCAEA-UHFFFAOYSA-N succinonitrile Chemical compound N#CCCC#N IAHFWCOBPZCAEA-UHFFFAOYSA-N 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
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- 239000000725 suspension Substances 0.000 description 1
- YBRBMKDOPFTVDT-UHFFFAOYSA-N tert-butylamine Chemical compound CC(C)(C)N YBRBMKDOPFTVDT-UHFFFAOYSA-N 0.000 description 1
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- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
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Abstract
通过由化学式(1)(1)(其中:Q-表示由无机酸或活泼氢化合物去除一个质子而形成的阴离子,该活泼氢化合物具有在氧、氮或硫原子上的活泼氢原子;a、b、c和d各是1或0,只是它们不全部是0;及多个R可以是相同或不同的,各独立地表示C1-10的烃基,或在一个共同氮原子上的存在两个R基团可相互连接并与该氮原子联合形成一种环状结构)表示的磷腈鎓盐化合物与具有一个或多个卤素原子的芳香卤代化合物反应,由Q(Q代表化学式(1)中显示的Q-移去一个电子形成的无机或有机基团)取代芳香卤代化合物中的至少一个卤素原子。这样,得到Q-取代的芳香族化合物。
Description
技术领域
本发明涉及取代芳香化合物的制备方法,取代芳香化合物是工业化学制品、聚合物、医药和农用化学制品等有用的产物或中间体,该制备方法是使用卤代芳香化合物、特别是可工业生产并可以低价格得到的氯代芳香化合物作起始原料,并用各种亲核物质取代上述氯代化合物中的氯原子。
技术背景
作为生产取代芳香化合物的方法之一,芳香族化合物的亲核取代反应是已知的,该反应中卤代芳香化合物和亲核试剂反应,用亲核物取代上述卤素原子,但也了解与脂肪族的卤代化合物比较,通常卤代芳香族化合物对亲核物具有明显低的反应性。然而,如果在芳香环的特殊位置上存在特殊的取代基,如在对-硝基氯苯、2,4-二硝基氯苯、或对-苯甲酰基氯苯(活性卤代芳香化合物)中,卤代芳香化合物的卤素原子对亲核取代的反应性明显地被该取代基活化而容易进行此反应。
另一方面,如在R.T.Morrison和R.N.Boyd著的“有机化学(日文译本最新卷)”第5版1289页中所述:“即使试图将卤代芳基化合物(在本发明中这是不活泼的卤代芳香化合物)或卤代乙烯基化合物用通常的亲核反应试剂处理而转变成酚、醚、胺或腈类,这将以失败告终”。在下列各文献中叙述了不活泼的卤代芳香化合物,例如氯苯、对-溴苯、邻-甲氧基碘代苯等中不存在这样的取代基,则不与亲核试剂反应,除非①该反应在非常剧烈的反应条件下进行,或②一旦将卤代化合物中卤素原子制成有机金属络合物可使其活化,在该络合物中芳香环是配体,或③存在一种制成的催化剂:①Fyfe,in Patai:“羟基的化学”第一部分,83-124页,Interscience出版公司,纽约,1971年;②Semmelhack和Hall,J.Am.Chem.Soc.,96卷,7091、7092页(1974);M.Fukui、Y.Endo和T.Oishi:Chem.Pharm.Bull.,28卷,3639页(1980年);或③A.A.Moroz和M.S.Shvartsberg,Russ.Chem.Rev.,43,679-689页(1974年);Mowry,Chem.Rev.,42,189-283(1948年),207-209页;S.L.Buchwald等,J.Am.Chem.Soc.,119,10539-10540页(1997年);S.L.Buchwald等:J.Am.Chem.Soc.,122,1360-1370页(2000年)。
在不活泼的卤代芳香化合物中,特别是与相应的非-氯代系列的卤代芳香化合物比较,氯代芳香化合物具有非常低的反应性且没有可利用的有效的反应试剂或催化剂。然而,因为上述氯代化合物可工业化生产并可以低廉的价格得到,近来,开发了实现不活泼氯代芳香化合物亲核取代反应的各种反应试剂和催化剂。例如在L.I.Goryunov和V.D.Shteingarts:Russ.J.Org.Chem,29卷,1849-1855页(1993年)中公开了使用昂贵的且不易工业化生产的Rh络合物作为催化剂及氯苯作原料,在反应温度80℃和180℃之间使氯苯反应4天~1小时,可得到苯甲醚,产率为60~75%。在美国专利5,315,043或美国专利6,087,543中公开了一种特殊的氟化试剂,与氯苯在温度210℃~450℃的非常剧烈条件下反应生产氟代苯,产率为6~70%。
发明内容
本发明的目的之一是提供一种有效的生产取代芳香化合物的方法,该方法在温和的反应条件下,使用对亲核取代反应非常有效的反应试剂,高产率地由卤代芳香化合物特别是氯代芳香化合物生产取代芳香化合物。
因此,本发明制备被Q取代的取代芳香化合物的方法包括:
将化学式(1)表示的磷腈鎓盐化合物:
(在此化学式中:
Q-表示无机酸或活泼氢化合物消去一个质子而衍生的阴离子,该活
泼氢化合物具有在氧原子、氮原子或硫原子上的活泼氢;
a、b、c和d各独立地为0或1,但它们不能同时全部是0;及
R基团表示相同或不同的具有1~10个碳原子的烃基,或在一个共同
氮原子上的两个R基团可连接在一起形成一种环状结构)与具有卤素原子的卤代芳香化合物反应;
由此,在卤代芳香化合物中至少一个卤素原子被Q(这里Q表示化学式(1)中的Q-消去一个电子而衍生的一种无机基团或一种有机基团)取代。
本发明者为了提供一种工业上顺利生产取代芳香化合物的方法而认真地进行了研究,结果发现通过使用化学式(1)磷腈鎓盐阳离子作为抗衡阳离子,明显地改进了由化学式(1)中Q-表示的各种亲核阴离子种类对芳香族化合物亲核取代反应的反应性。发明者发现使用由化学式(1)表示的磷腈鎓盐化合物,不活泼的卤代芳香化合物,特别是不活泼的氯代芳香化合物的亲核取代反应可在非常温和条件下进行,并可以高产率得到作为目标的取代芳香化合物,而该反应按照惯例被认为是不易进行的。因此完成了本发明。
具体而言,例如在下文叙述的实施例1和实施例2中所示,令人惊奇地发现{四[三(二甲氨基)正膦亚基氨基]鏻}甲醇盐:[(Me2N)3P=N]4P+MeO-(Me在化学式和下列叙述中表示甲基)易于与氯苯在室温反应以95%的产率生产所需要的苯甲醚,以及使用氟化{四[三(二甲氨基)正膦亚基氨基]鏻}:[(Me2N)3P=N]4P+F-与氯苯在130℃下反应以81%的产率生产氟代苯,与常规条件比较该反应条件是非常温和的。
此外在本发明的一个方面,当进行由Q-的取代反应时,可使用由化学式(2)表示的磷腈鎓盐化合物:
(在此化学式中,Z-是卤素阴离子及a、b、c、d和R基团与上述含义相同)和一种由MQn(在该化学式中M表示碱金属原子、碱土金属原子、或稀土金属原子,Q与上述含义相同,及n是1~3的整数)表示的金属化合物作原料,使它们相互接触,在反应体系中产生由上述化学式(1)表示的磷腈鎓盐化合物,这样可实施上述取代反应。
附图简述
图1是表示实施例21和比较例1~3中对-氟硝基苯反应速率的曲线图。
实施本发明的最佳模式
虽然用于本发明的化学式(1)或(2)的磷腈鎓盐化合物是典型地由规范化学式(即化学式(1)或化学式(2))表示的,其中磷腈鎓盐阳离子的正电荷定位于中心磷原子上,但可用不同于该化学式的无数其他规范化学式来描述,且正电荷事实上并非是完全定位的。
在衍生阴离子Q-的化合物之中,无机酸的实例包括:包括例如氟化氢、氯化氢、溴化氢或碘化氢的卤化氢;氢氰酸;硫氰酸;叠氮化氢等。
在衍生阴离子Q-的化合物之中,在氧原子上具有活泼氢原子的活性化合物的实例包括:水;具有1~20个碳原子的羧酸包括例如甲酸、乙酸、丙酸、丁酸、异丁酸、月桂酸、硬脂酸、油酸、苯乙酸、二氢肉桂酸、环己烷羧酸、苯甲酸、对甲基苯甲酸和2-羧基萘;具有2~20个碳原子及2~6个羧基的多价羧酸,包括例如草酸、丙二酸、丁二酸、顺丁烯二酸、反丁烯二酸、己二酸、衣康酸、丁烷四甲酸、邻苯二酸、间苯二酸、对苯二酸、偏苯三酸和均苯四酸;氨基甲酸包括例如N,N-二乙基氨基甲酸、N-羧基吡咯烷酮、N-羧基苯胺和N,N′-二羧基-2,4-甲苯二胺;具有1~20个碳原子的醇,包括例如甲醇、乙醇、正丙醇、异丙醇、正丁醇、仲丁醇、叔丁醇、异戊醇、叔戊醇、正辛醇、月桂醇、十六烷醇、环戊醇、环己醇、烯丙醇、巴豆醇、甲基乙烯基甲醇、苄醇、1-苯基乙醇、三苯基甲醇和肉桂醇;具有2~20个碳原子和2~8个羟基的多羟基醇,包括例如乙二醇、丙二醇、二甘醇、双丙甘醇、1,3-丙二醇、1,3-丁二醇、1,4-丁二醇、1,6-己二醇、1,4-环己烷二醇、三羟甲基丙烷、甘油、双甘油、季戊四醇和二聚季戊四醇;具有6~20个碳原子和1~3个羟基的芳香化合物,包括例如苯酚、2-萘酚、2,6-二羟基萘和双酚A;及其他。
在衍生阴离子Q-的化合物之中,在氮原子上具有活泼氢原子的活泼氢化合物的实例包括:具有1~20个碳原子脂肪族或芳香族伯胺,包括例如甲胺、乙胺、正丙胺、异丙胺、正丁胺、异丁胺、仲丁胺、叔丁胺、环己胺、苄胺、β-苯基乙胺、苯胺、邻-甲苯胺、间-甲苯胺和对-甲苯胺;具有2~20个碳原子的脂肪族或芳香族仲胺,包括例如二甲基胺、甲基乙基胺、二乙基胺、二-正-丙基胺、乙基-正-丁基胺、甲基-仲-丁基胺、二戊基胺、二环己基胺、N-甲基苯胺和二苯基胺;具有2~20个碳原子和2~3个伯氨基或仲氨基的多价胺,包括例如乙二胺、二(2-氨基乙基)胺、1,6-己二胺、4,4′-二氨基二苯基甲烷、三(2-氨基乙基)胺、N,N′-二甲基乙二胺、N,N′-二乙基乙二胺和二(2-甲基氨基乙基)胺;具有4~20个碳原子的饱和环状仲胺,包括例如吡咯烷、哌啶、吗啉和1,2,3,4-四氢喹啉;具有4~20个碳原子的不饱和的环状仲胺,包括例如3-吡咯啉、吡咯、吲哚、咔唑、咪唑、吡唑和嘌呤;具有4~20个碳原子和2~3个仲氨基的环状多价胺,包括例如哌嗪、吡嗪及1,4,7-三氮杂环壬烷;具有2~20个碳原子的未取代或N-单取代酰胺,包括例如乙酰胺、丙酰胺、N-甲基丙酰胺、N-甲基苯甲酰胺和N-乙基硬脂酰胺;五~七-元环的环状酰胺,包括例如2-吡咯烷酮和-己内酰胺;具有4~10个碳原子的二羧酸酰亚胺,包括例如丁二酰亚胺、顺丁烯二酰亚胺及苯邻二甲酰亚胺。
在衍生阴离子Q-的化合物之中,在硫原子上具有活泼氢原子的活泼氢化合物的实例包括:单价硫醇,包括例如甲硫醇、乙硫醇、正-丁硫醇、叔-丁硫醇、己硫醇、癸硫醇、环戊硫醇和环己硫醇;多价硫醇,包括例如1,2-乙二硫醇、1,3-丙二硫醇、2,3-丁二硫醇、1,6-己二硫醇,1,2,3-丙三硫醇和2,3-二(巯基甲基)-1,4-丁二硫醇;芳香族巯基化合物,包括例如苯硫酚、邻-甲苯硫酚、萘硫酚和1,2-苯二硫酚。
上述活泼氢化合物包括具有多个活泼氢原子的化合物。多个活泼氢原子全部可消去而形成阴离子,但也可消去部分原子形成阴离子。
而且,作为阴离子Q-,只要它不妨碍本发明的方法,任何阴离子都可以是合格的。
在衍生阴离子Q-的化合物之中,优选化合物的实例包括:卤化氢,包括例如氟化氢、氯化氢、溴化氢和碘化氢;氢氰酸、硫氰酸、水;具有1~20个碳原子的羧酸,包括例如甲酸、乙酸、丙酸、丁酸、异丁酸、月桂酸、硬脂酸、油酸、苯乙酸、二氢肉桂酸、环己烷羧酸、苯甲酸、对甲基苯甲酸和2-羧基萘;具有1~20个碳原子的醇,包括例如甲醇、乙醇、正丙醇、异丙醇、正丁醇、仲丁醇、叔丁醇、异戊醇、叔戊醇、正辛醇、月桂醇、十六烷醇、环戊醇、环己醇、烯丙醇、巴豆醇、甲基乙烯基甲醇、苄醇、1-苯基乙醇、三苯基甲醇和肉桂醇;具有6~20个碳原子和1~3个羟基的芳香化合物,包括例如苯酚、2-萘酚、2,6-二羟基萘和双酚A;具有2~20个碳原子的脂肪族或芳香族仲胺,包括例如二甲胺、甲基乙基胺、二乙胺、二-正丙基胺、乙基-正丁基胺、甲基-仲丁基胺、二戊基胺、二环己基胺、N-甲基苯胺和二苯基胺;单价硫醇,包括例如甲硫醇、乙硫醇、正-丁硫醇、叔-丁硫醇、己硫醇、癸硫醇、环戊硫醇和环己硫醇;芳香族巯基化合物,包括例如苯硫酚、邻-甲苯硫酚、萘硫酚和1,2-苯二硫酚。
更优选的化合物包括:例如氟化氢、氢氰酸、硫氰酸、水;具有1~20个碳原子的羧酸,包括例如甲酸、乙酸、丙酸、丁酸、异丁酸、月桂酸、硬脂酸、油酸、苯乙酸、二氢肉桂酸、环己烷羧酸、苯甲酸、对甲基苯甲酸和2-羧基萘;具有6~20个碳原子和1~3个羟基的芳香化合物,包括例如苯酚、2-萘酚、2,6-二羟萘和双酚A;单价硫醇,包括例如甲硫醇、乙硫醇、正-丁硫醇、叔-丁硫醇、己硫醇、癸硫醇、环戊基硫醇和环己基硫醇;芳香族巯基化合物,包括例如苯硫酚、邻-甲苯硫酚、萘硫酚和1,2-苯二硫酚。
化学式(1)中(同样在化学式(2)中)a、b、c和d各是0或1。然而,它们不能全部同时为0。优选a、b、c和d中至少三个是1。这意味着不管顺序如何,其综合数目为(1,1,1,1)或(0,1,1,1),更优选a、b、c和d全部是1。
化学式(1)中(同样在化学式(2)中)R基团可全部相同或相互不同。“R2”表达的两个R基团可以相互不同。以及R可独立地表示具有1~10个碳原子的烃基,或在相同氮原子上的两个R基团可相互连接与氮原子一起形成环。
当R单独表示一个烃基时,它选自脂肪族或芳香族烃基,包括例如甲基、乙基、正-丙基、异丙基、烯丙基、正-丁基、仲-丁基、叔-丁基、2-丁烯基、1-戊基、2-戊基、3-戊基、2-甲基-1-丁基、异戊基、叔-戊基、3-甲基-2-丁基、新戊基、正-己基、4-甲基-2-戊基、环戊基、环己基、1-庚基、3-庚基、1-辛基、2-辛基、2-乙基-1-己基、1,1-二甲基-3,3-二甲基丁基(通俗名称为叔-辛基)、壬基、癸基、苯基、4-甲苯基、苄基、1-苯基乙基和2-苯基乙基。这些基团之中,优选具有1~10个碳原子的脂肪族烃基,包括甲基、乙基、正-丙基、异丙基、叔-丁基、叔-戊基或1,1-二甲基-3,3-二甲基丁基,以及更优选甲基。
当在相同氮原子上的两个R基团连接在一起形成一个环并成为二价取代基的情况下,该二价取代基的主链优选具有4~6个碳原子的二价烃基(此环成为五~七-元环),例如,1,4-亚丁基、1,5-亚戊基,1,6-亚己基等,或优选在其主链上被烷基如甲基,乙基等取代的那些基团。更优选的是1,4-亚丁基或1,5-亚戊基。
磷腈鎓盐阳离子中全部或部分任意可能存在的氮原子可以是具有如此环状结构的氮原子。当部分R基团形成环状结构时,其余的R基团可以是上述R单独表示烃基情况的基团,以及优选的基团也与上述相同。
这些磷腈鎓盐化合物可根据EP 0791600中12~13页叙述的方法、或与此方法类似的方法来合成。
用于本发明的卤代芳香化合物是具有至少一个卤素原子在芳香环上的化合物,及其可任意是芳香族烃类化合物或是芳香族的杂环化合物。
当卤代芳香化合物具有多个卤素原子时,这些原子中至少一个参与取代反应并被Q取代就足够了。此外,芳香化合物从开始就可以有Q基团,在这种情况下,在卤素被本方法Q取代后,所得到的这种化合物中的Q的数量将进一步增加一个或一个以上。
卤代芳香族烃类化合物的实例包括不活泼的氟代芳香族烃类化合物、不活泼的氯代芳香族烃类化合物、不活泼的溴代芳香族烃类化合物、不活泼的碘代芳香族烃类化合物、活泼的氟代芳香族烃类化合物、活泼的氯代芳香族烃类化合物、活泼的溴代芳香族烃类化合物和活泼的碘代芳香族烃类化合物。
这里,不活泼的和活泼的卤代芳香族烃类化合物是根据R.T.Morrison和R.N.Boyd著的“有机化学(日文译本最新卷)”第5版1298~1301页中所述定义的。即卤代芳香族烃类化合物中在卤素原子的邻-位和/或对-位有受电子基团取代,该卤代芳香族烃类化合物被定义为活泼的卤代芳香族烃类化合物,以及除此以外的任何化合物,即卤代芳香族烃类化合物中在卤素原子的邻-位和/或对-位没有受电子基团取代,该卤代芳香族烃类化合物被定义为不活泼的卤代芳香族烃类化合物。
不活泼的氟代芳香族烃类化合物的实例包括:氟代苯、2-氟甲苯、3-氟甲苯、4-氟甲苯、2-甲氧基氟代苯、3-甲氧基氟代苯、4-甲氧基氟代苯、2-二甲氨基氟代苯、3-二甲氨基氟代苯、4-二甲氨基氟代苯、2-羟基氟代苯、3-羟基氟代苯、4-羟基氟代苯、2-氨基氟代苯、3-氨基氟代苯、4-氨基氟代苯、1,3-二氟代苯、1,3,5-三氟代苯、3-硝基氟代苯、3-氰基氟代苯、3-苯磺酰基-氟代苯、3-乙氧羰基-氟代苯,3-甲酰基氟代苯、3-苯甲酰基-氟代苯,1-氟代萘、2-氟代萘等。
不活泼的氯代芳香族烃类化合物的实例包括:氯苯、2-氯代甲苯、3-氯代甲苯、4-氯代甲苯、2-甲氧基氯苯、3-甲氧基氯苯、4-甲氧基氯苯、2-二甲氨基氯苯、3-二甲氨基氯苯、4-二甲氨基氯苯、2-羟基氯苯、3-羟基氯苯、4-羟基氯苯、2-氨基氯苯、3-氨基氯苯、4-氨基氯苯、1,3-二氯苯、1,3,5-三氯苯、3-硝基氯苯、3-氰基氯苯、3-苯磺酰基-氯苯、3-乙氧羰基-氯苯、3-甲酰基氯苯、3-苯甲酰基-氯苯、1-氯代萘、2-氯代萘等。
不活泼的溴代芳香族烃类化合物的实例包括:溴苯、2-溴代甲苯、3-溴代甲苯、4-溴代甲苯、2-甲氧基溴苯、3-甲氧基溴苯、4-甲氧基溴苯、2-二甲氨基溴苯、3-二甲氨基溴苯、4-二甲氨基溴苯、2-羟基溴苯、3-羟基溴苯、4-羟基溴苯、2-氨基溴苯、3-氨基溴苯、4-氨基溴苯、1,3-二溴苯、1,3,5-三溴苯、3-硝基溴苯、3-氰基溴苯、3-苯磺酰基-溴苯、3-乙氧羰基-溴苯、3-甲酰基溴苯、3-苯甲酰基-溴苯、1-溴代萘、2-溴代萘等。
不活泼的碘代芳香族烃类化合物的实例包括:碘代苯、2-碘代甲苯、3-碘代甲苯、4-碘代甲苯、2-甲氧基碘代苯、3-甲氧基碘代苯、4-甲氧基碘代苯、2-二甲氨基碘代苯、3-二甲氨基碘代苯、4-二甲氨基碘代苯、2-羟基碘代苯、3-羟基碘代苯、4-羟基碘代苯、2-氨基碘代苯、3-氨基碘代苯、4-氨基碘代苯、1,3-二碘代苯、1,3,5-三碘代苯、3-硝基碘代苯、3-氰基碘代苯、3-苯磺酰基-碘代苯、3-乙氧羰基-碘代苯、3-甲酰基碘代苯、3-苯甲酰基-碘代苯、1-碘代萘、2-碘代萘等。
活泼的氟代芳香族烃类化合物的实例包括:2-硝基氟代苯、4-硝基氟代苯、2-氰基氟代苯、4-氰基氟代苯、2-苯磺酰基-氟代苯、4-苯磺酰基-氟代苯、4-乙氧羰基-氟代苯、4-甲酰基氟代苯、4-苯甲酰基-氟代苯、2,4-二硝基氟代苯、2-氰基-4-硝基氟代苯,2,4-二氰基氟代苯、1,2-二氟代苯、1,2,4-三氟代苯、六氟代苯、1,2-二氟代萘、1,2,4-三氟代萘、八氟萘、4,4′-二氟二苯甲酮、4,4′-二氟二苯砜等。
活泼的氯代芳香族烃类化合物的实例包括:2-硝基氯苯、4-硝基氯苯、2-氰基氯苯、4-氰基氯苯、2-苯磺酰基-氯苯、4-苯磺酰基-氯苯、4-乙氧羰基-氯苯、4-甲酰基氯苯、4-苯甲酰基-氯苯、2,4-二硝基氯苯、2-氰基-4-硝基氯苯、2,4-二氰基氯苯、1,2-二氯苯、1,2,4-三氯苯、六氯苯、1,2-二氯萘、1,2,4-三氯萘、八氯萘、4,4′-二氯二苯甲酮,4,4′-二氯二苯砜等。
活泼的溴代芳香族烃类化合物的实例包括:2-硝基溴苯、4-硝基溴苯、2-氰基溴苯、4-氰基溴苯、2-苯磺酰基-溴苯、4-苯磺酰基-溴苯、4-乙氧羰基-溴苯、4-甲酰基溴苯、4-苯甲酰基-溴苯、2,4-二硝基溴苯、2-氰基-4-硝基溴苯、2,4-二氰基溴苯、1,2-二溴苯、1,2,4-三溴苯、六溴苯、1,2-二溴萘、1,2,4-三溴萘、八溴萘、4,4′-二溴二苯甲酮、4,4′-二溴二苯砜等。
活泼的碘代芳香族烃类化合物的实例包括:2-硝基碘代苯、4-硝基碘代苯、2-氰基碘代苯、4-氰基碘代苯、2-苯磺酰基-碘代苯、4-苯基磺酰基-碘代苯、4-乙氧羰基-碘代苯、4-甲酰基碘代苯、4-苯甲酰基-碘代苯、2,4-二硝基碘代苯、2-氰基-4-硝基碘代苯、2,4-二氰基碘代苯、1,2-二碘代苯、1,2,4-三碘代苯、六碘代苯、1,2-二碘代萘、1,2,4-三碘代萘、八碘代萘、4,4′-二碘二苯甲酮、4,4′-二碘二苯砜等。
芳香族杂环化合物是例如氟代、氯代、溴代或碘代芳香族杂环化合物。
氟代芳香族杂环化合物的实例包括:2-氟代呋喃、3-氟代呋喃、5-氟代糠醛、2-氟代噻吩、3-氟代噻吩、2,5-二氟噻吩、3,4-二氟噻吩、四氟噻吩、2-乙酰基-5-氟代噻吩,3-乙酰基-2,5-氟代噻吩、4-氟-2-噻吩甲醛、5-氟-2-噻吩甲醛、4-氟代吡唑、4-氟-3-甲基吡唑、5-氟-3-甲基-1-苯基-4-吡唑甲醛、5-氟-1-甲基咪唑、2-氟代噻唑、3,4-二氟代噻唑、4-氟代吲哚、5-氟代吲哚、5-氟代吲哚乙酸盐、2,4,8-三氟代苯并呋喃、2-氟代苯并咪唑、5-氟代苯并三唑、5-氟-2-甲基苯并噁唑、2-氟代吡啶、3-氟代吡啶、2,5-二氟代吡啶、6-氟代吡啶酚、2-氟-5-硝基吡啶、氟代吡嗪、4-氟-喹啉、6-氟-喹啉等。
对于氯代芳香族的杂环化合物,上述氟代芳香族杂环化合物中的氟原子被氯原子取代的化合物、二氧芑等可作为实例。对于溴代芳香族杂环化合物和碘代芳香族杂环化合物,上述氟代芳香族杂环化合物中的氟原子分别被溴和碘取代的化合物可作为实例。
在上文中,虽然为方便分类,仅举例说明了在同一分子中有一种卤素原子的化合物,但在本发明中,卤代芳香化合物不受这些说明所限制,可在同一分子中具有2种或多种不同类的卤素原子,且更进一步这些卤代芳香化合物可具有任何取代基、功能团或杂原子,只要本发明方法受阻碍。
这些卤代芳香化合物优选上述不活泼的氟代芳香族烃类化合物、不活泼的氯代芳香族烃类化合物、不活泼的溴代芳香族烃类化合物、活泼的氟代芳香族烃类化合物、活泼的氯代芳香族烃类化合物、活泼的溴代芳香族烃类化合物、氯代芳香族杂环化合物或溴代芳香族杂环化合物,以及更优选不活泼的氟代芳香族烃类化合物、不活泼的氯代芳香族烃类化合物、不活泼的溴代芳香族烃类化合物、氯代芳香族杂环化合物或溴代芳香族杂环化合物。此外,不活泼的氯代芳香族烃类化合物、氯代芳香族杂环化合物或溴代芳香族杂环化合物是特别优选的。
在本发明中,当Q是卤素时,在用于反应的卤代芳香化合物中参与交换反应的卤素必须是周期表中在Q以下部分的元素中的一种。即如果Q-是F-,例如可使用的卤代芳香化合物是具有至少一个氯、溴或碘原子的卤代芳香化合物。
因此,如果Q-是F-,卤代芳香化合物选自上述不活泼的或活泼的氯代、溴代或碘代芳香族烃类化合物,和氯代、溴代或碘代芳香族杂环化合物等。优选不活泼的氯代芳香族烃类化合物、不活泼的溴代芳香族烃类化合物、活泼的氯代芳香族烃类化合物、活泼的溴代芳香族烃类化合物、氯代芳香族杂环化合物和溴代芳香族杂环化合物,更优选不活泼的氯代芳香族烃类化合物、不活泼的溴代芳香族烃类化合物、氯代芳香族杂环化合物和溴代芳香族杂环化合物,及此外还更优选不活泼的氯代芳香族烃类化合物、氯代芳香族杂环化合物或溴代芳香族杂环化合物。
由化学式(1)表示的磷腈鎓盐化合物所使用的数量不是特别限制的,但该数量通常是卤代芳香化合物中被取代卤素原子的5摩尔或5摩尔以下到1摩尔,优选0.5~2摩尔,及更优选0.8~1.2摩尔。
反应温度依赖于化学式(1)表示的磷腈鎓盐化合物的种类和所使用的卤代芳香化合物或溶剂(如果使用),而不必限定,但通常是250℃或250℃以下,优选0~230℃,及更优选30~200℃。反应期间的压力依赖于所使用原料的种类及其他而不必限定,但通常是3.0兆帕(绝对压力,下文所述相同)或3.0兆帕以下,优选0.01~1.5兆帕,及更优选0.1~1.0兆帕。反应时间通常是48小时以内,优选0.01~30小时,及更优选0.02~15小时。
此外,在本发明的一个方面,当由Q-的取代反应进行时,使用由化学式(2)表示的磷腈鎓盐化合物:
(此化学式中,Z-是卤素阴离子,及a、b、c、d和R基团与上述含义相同)和由MQn(在此化学式中,M表示碱金属原子、碱土金属原子或稀土金属原子,Q与上述含义相同,及n是1~3的整数)表示的金属化合物作原料,使它们相互接触,在反应体系中产生上述的化学式(1)表示的磷腈鎓盐化合物,及这样可进行上述取代反应。
这里,有关化学式(2)表示的磷腈鎓盐化合物的a、b、c、d和R基团的条件、优选条件及其他,和上述化学式(1)所需的a、b、c、d和R基团的条件相同。
Z-是卤素阴离子,例如氟阴离子、氯阴离子、溴阴离子、碘阴离子等,及在它们之中优选氟阴离子和氯阴离子,及更优选氯阴离子。
在此反应中,当在反应体系中产生的化学式(1)的[磷腈鎓盐阳离子]+Q-中Q-被与卤代芳香化合物的反应所消耗时,Q由MQn补给。因此优点是所使用化学式(2)的[磷腈鎓盐阳离子]+Z-的数量非常小。而且,在Z-和Q-相同的情况下,当先前供入的Z-(=Q-)消耗时,Q-由MQn补给,因此即使在Z-与Q-相同时,也有有利的效果。
由化学式(2)表示的这些磷腈鎓盐化合物可两种或两种以上合起来使用。此外按照惯例用作催化剂的大环聚醚(冠醚等)、链状聚醚、季铵盐、季鏻盐等可与这些由化学式(2)表示的磷腈鎓盐化合物一起使用。
由MQn表示的金属化合物中的M可以是取化合价数高达三价的金属。
实例包括:碱金属原子包括例如锂、钠、钾、铯或铷;碱土金属原子包括例如镁、钙、锶或钡;稀土金属原子包括例如铈、镨、钕或钐。它们之中,优选碱金属原子包括例如锂、钠、钾、铯或铷,及更优选钠和钾。
n是1~3的整数,及优选1。
由化学式(2)表示的磷腈鎓盐化合物所使用的量没有特别的限制。然而该数量低于卤代芳香化合物中被取代卤素原子的摩尔数就足够了。因此,对每1摩尔被取代的卤素原子,该数量通常为1摩尔或1摩尔以下,优选在0.001~0.2摩尔的范围,及更优选在0.01~0.1摩尔的范围。
虽然金属化合物MQn所使用的量没有特别的限制,对每1摩尔卤代芳香化合物中被取代的卤素原子,MQn中可交换Q的摩尔数(通常它们可交换n个)通常在0.5~4.0摩尔的范围。优选在0.8~2.5摩尔的范围,及更优选在1.0~1.5摩尔的范围(MQn的摩尔数是该数字的1/n)。
反应温度、反应压力和反应时间与使用上述化学式(1)磷腈鎓盐化合物时相同。
在本发明中,反应可在不使用溶剂的情况下完成。但如果需要可以使用溶剂,以确保化学式(1)或化学式(2)表示的磷腈鎓盐化合物和卤代芳香化合物的有效接触,及在MQn表示的金属化合物存在的情况下与金属化合物的有效接触。
在这种情况下,所使用的溶剂依赖于这些所使用化合物的种类或数量而不必限定。可使用任何溶剂,只要它不妨碍反应。溶剂的实例包括脂肪族或芳香族烃类,包括例如正-戊烷、正-己烷、环己烷、苯、甲苯、二甲苯、1,2,3,4-四氢化萘、萘、氯苯、氯甲苯、邻-二氯苯、3,4-二氯甲苯和1-氯代萘;醚类包括例如乙醚、四氢呋喃、1,4-二噁烷、乙二醇二甲醚、三甘醇二甲基醚、聚乙二醇、聚丙二醇和二苯醚;酮类包括例如丙酮、甲基乙基酮、二异丙基酮和二苯甲酮;叔胺类包括例如三丁胺、N,N-二甲基苯胺、吡啶和喹啉;硝基化合物类包括例如硝基甲烷、硝基乙烷、硝基苯和邻-硝基甲苯;腈类包括例如乙腈、丙腈、1,2-二氰基乙烷和苄腈;对质子惰性的极性溶剂包括例如N,N-二甲基甲酰胺、N-甲基吡咯烷酮、二甲亚砜、二甲砜、二苯亚砜、二苯砜、环丁砜、六甲替磷酰三胺和1,3-二甲基-2-咪唑啉酮。这些溶剂可任意单独使用或使用2种或多种的混合物。
在本发明方法中,从反应混合物中分离目标取代芳香化合物的方法依赖于所使用原料的种类、目标芳香族取代化合物的种类或所使用溶剂的种类及数量,而不必是限定的。但通常地,目标芳香族取代化合物可通过使用萃取、蒸馏、重结晶、柱层析等任何方法,从反应混合物溶液中得到,或在使用溶剂的情况下,在去除溶剂后,从反应混合物中得到。
实施例
实施例1
在氮气气氛下将7.7lg(10.0毫摩尔)磷腈鎓盐化合物{四[三(二甲氨基)正膦亚基氨基]鏻}甲醇盐[(Me2N)3P=N]4P+MeO-称入装有温度计的100ml烧瓶后,在室温加入20.0g(178毫摩尔)氯苯。混合物在室温反应2小时后,从该反应混合物中取出少量样品用气相色谱分析。作为结果,除了氯苯的峰,惊奇地观察到一个新峰,该峰有相当大的积分强度。对该反应混合物进行GC-Mass(带气相色谱的质谱分析仪)分析,检测到108和77的峰分别显示苯甲醚的分子离子峰及消去甲氧基后苯基的碎片离子峰。此结果显示新峰是苯甲醚。
此外,重复进行上述反应操作并得到反应混合物。从反应混合物取出少量样品,用气相色谱以1,2,3-三氯苯作内标,进行苯甲醚的定量分析。作为结果,发现所生成苯甲醚的产率为95%。然后,反应混合物用20ml的1N盐酸溶液和20ml水洗后,分离出的有机相液体用小精馏装置蒸馏,得到目标化合物苯甲醚0.961g(产率89%)。该产物的IR、1H-NMR和13C-NMR的测量图与参照标准一致。
实施例2
在氮气气氛下将7.59g(10.0毫摩尔)磷腈鎓盐化合物氟化{四[三(二甲氨基)正膦亚基氨基]鏻}[(Me2N)3P=N]4P+F-称入体积为100ml并装有温度计的压力玻璃容器后,室温加入20.0g(178毫摩尔)氯苯,将容器密封。此溶液加热到130℃并在该温度下反应2小时。然后与实施例1相同,从得到的反应混合物中取出少量样品用气相色谱定量分析,作为结果,发现所生成的目标化合物氟代苯的产率为81%。
实施例3
反应与实施例1相同的方式进行,除了用相同摩尔数的{四[三(二甲氨基)正膦亚基氨基]鏻}叔-丁基硫醇盐[(Me2N)3P=N]4P+t-BuS-代替实施例1的{四[三(二甲氨基)正膦亚基氨基]鏻}甲醇盐。然后,用类似的气相色谱方法进行定量分析。作为结果发现所生成的目标化合物叔-丁基苯基硫醚的产率为99%。
实施例4
反应与实施例2完全相同的方式进行,除了用氰化{四[三(二甲氨基)正膦亚基氨基]鏻}[(Me2N)3P=N]4P+CN-代替实施例2的氟化{四[三(二甲氨基)正膦亚基氨基]鏻}。发现生成目标化合物苄腈的产率为94%。
实施例5
反应与实施例2完全相同的方式进行,除了用硫氰酸{四[三(二甲氨基)正膦亚基氨基]鏻}盐[(Me2N)3P=N]4P+SCN-代替实施例2中的氟化{四[三(二甲氨基)正膦亚基氨基]鏻}。发现生成目标化合物异硫氰酸苯酯的产率为90%。
实施例6
反应与实施例2完全相同的方式进行,除了用氢氧化{四[三(二甲氨基)正膦亚基氨基]鏻}[(Me2N)3P=N]4P+OH-代替实施例2中的氟化{四[三(二甲氨基)正膦亚基氨基]鏻}及反应温度改变为150℃外。发现生成目标化合物苯酚的产率为41%。
实施例7
反应与实施例2完全相同的方式进行,除了用苯甲酸{四[三(二甲氨基)正膦亚基氨基]鏻}盐[(Me2N)3P=N]4P+C6H5COO-代替实施例2中的氟化{四[三(二甲氨基)正膦亚基氨基]鏻}及反应温度改变为150℃外。发现生成目标化合物苯甲酸苯酯的产率为31%。
实施例8
反应与实施例2完全相同的方式进行,除了用{四[三(二甲氨基)正膦亚基氨基]鏻}苯酚盐[(Me2N)3P=N]4P+C6H5O-代替实施例2中的氟化{四[三(二甲氨基)正膦亚基氨基]鏻}及反应温度改变为160℃外。发现生成目标化合物二苯醚的产率为61%。
实施例9
反应与实施例2完全相同的方式进行,除了用{四[三(二甲氨基)正膦亚基氨基]鏻}苯硫酚盐[(Me2N)3P=N]4P+C6H5S-代替实施例2中的氟化{四[三(二甲氨基)正膦亚基氨基]鏻}、使用4-氯代甲苯代替实施例2中的氯苯及反应温度改变为160℃外。发现生成目标化合物4-甲基二苯硫醚的产率为88%。
实施例10
反应与实施例1中完全相同的方式进行,除了用{四[三(二甲氨基)正膦亚基氨基]鏻}二-正丙基氨盐[(Me2N)3P=N]4P+(C3H7)2N-代替实施例1中的{四[三(二甲氨基)正膦亚基氨基]鏻}甲醇盐。发现生成目标化合物二-正丙氨基苯的产率为91%。
实施例11
反应与实施例2完全相同的方式进行,除了用1,2-二氯苯代替实施例2中的氯苯。生成目标化合物2-氯代氟苯的产率为92%。
实施例12
反应与实施例2完全相同的方式进行,除了用1,3-二氯苯代替实施例2中的氯苯。生成目标化合物3-氯代氟苯的产率为74%。
实施例13
反应与实施例2完全相同的方式进行,除了用1,3-二溴苯代替实施例2中的氯苯。生成目标化合物3-溴代氟苯的产率为85%。
实施例14
反应与实施例2完全相同的方式进行,除了用3-氯代氟苯代替实施例2中的氯苯。生成目标化合物1,3-二氟代苯的产率为77%。
实施例15
反应与实施例1完全相同的方式进行,除了用1,3-二氯苯代替实施例1中的氯苯。生成目标化合物3-氯代苯甲醚的产率为92%。
实施例16
反应与实施例1完全相同的方式进行,除了用{三[三(二甲氨基)正膦亚基氨基][(二辛基氨基)正膦亚基氨基]鏻}乙醇盐[(Me2N)3P=N]3P+{N=P[N(C8H17)2]}C2H5O-代替实施例1中的{四[三(二甲氨基)正膦亚基氨基]鏻}甲醇盐。生成目标化合物苯乙醚的产率为86%。
实施例17
将7.71g(10.0毫摩尔){四[三(二甲氨基)正膦亚基氨基]鏻}甲醇盐称入体积为100ml并装有温度计的压力玻璃容器后,室温加入30ml无水四氢呋喃(下文将简称为THF)和1.66g(10.0毫摩尔)1-甲基-6-氯代吲哚。混合物在室温反应16小时后,从该反应混合物中取出少量样品用气相色谱分析。发现生成目标化合物1-甲基-6-甲氧基吲哚的产率为89%。
实施例18
反应与实施例17完全相同的方式进行,除了用2.5倍摩尔数量的氟化{四[三(二甲氨基)正膦亚基氨基]鏻}代替实施例1 7中的{四[三(二甲氨基)正膦亚基氨基]鏻}甲醇盐、用相同摩尔数量的1,2-二氯苯代替1-甲基-6-氯代吲哚、以及反应温度改变为130℃外。生成目标化合物1,2-氟代苯的产率为92%。
实施例19
反应与实施例17完全相同的方式进行,除了用2.5倍摩尔数量的氟化{四[三(二甲氨基)正膦亚基氨基]鏻}代替实施例17中的{四[三(二甲氨基)正膦亚基氨基]鏻}甲醇盐、用等摩尔数量的4,4′-二氯二苯甲酮代替1-甲基-6-氯代吲哚、及用甲苯代替THF外。此外反应温度改变为70℃。生成目标化合物4,4′-二氟二苯甲酮的产率为99%。
实施例20
反应与实施例17完全相同的方式进行,除了用氟化{四[三(二甲氨基)正膦亚基氨基]鏻}代替实施例17中的{四[三(二甲氨基)正膦亚基氨基]鏻}甲醇盐、用4-溴代吡啶代替1-甲基-6-氯代吲哚及用甲苯代替THF外。此外反应温度改变为130℃。生成目标化合物4-氟代吡啶的产率为89%。
实施例21
在氮气气氛下往装有温度计和冷凝器的100-ml烧瓶中供入2.36g(15.0毫摩尔)对-氯代硝基苯、Wako纯粹化学工业有限公司喷雾-干燥方法生产的1.31g(22.5毫摩尔)氟化钾(对应于MQn的化合物)、0.55g(0.75毫摩尔)由循环干燥氮气在100℃充分干燥的磷腈鎓盐化合物氯化{四[三(二甲氨基)正膦亚基氨基]鏻}[(Me2N)3P=N]4P+Cl-、及10.4g无水二甲亚砜(下文简称为DMSO)。该悬浮液搅拌下在大约10分钟加热到150℃。然后与实施例1类似,在30分钟后、1小时后、3小时后及6小时后,从反应混合物中取出少量样品用气相色谱进行定量分析。作为结果,发现生成对-氟硝基苯的产率对应于各反应时间为33%、50%、83%及98%。此后,将反应混合物冷却到室温,过滤分离不溶性固体。用10ml甲苯将这些固体洗两次,洗出液与母液层混合。该溶液用50ml水洗3次后,有机相用硫酸钠干燥,然后减压蒸馏除去甲苯。作为结果,得到1.87g几乎纯净的油状物对-氟硝基苯。
即使以小数量如催化剂量使用磷腈鎓盐化合物,取代反应可通过与相应MQn的化合物一起使用来进行,且更惊奇地发现产生对-氟硝基苯的反应速率,与比较例1中出示的非催化条件下的反应速率比较增加了12倍或12倍以上,此外与比较例2或3出示的使用常规催化剂反应速率比较增加了大约10倍。这些结果在图1中表示。
比较例1
除了没有使用实施例21中的磷腈鎓盐化合物氯化{四[三(二甲氨基)正膦亚基氨基]鏻外,用实施例21中相同的方式进行反应和定量分析。在30分钟后、1小时后、3小时后和6小时后对-氟硝基苯的产率分别为4%、7%、15%和24%。
比较例2
除了用相同摩尔数的溴化四苯基鏻代替实施例21中的磷腈鎓盐化合物氯化{四[三(二甲氨基)正膦亚基氨基]鏻}外,用实施例21中相同的方式进行反应和定量分析。在30分钟后、1小时后、3小时后和6小时后对-氟硝基苯的产率分别为6%、12%、27%和38%。
比较例3
除了用相同摩尔数的18-冠醚-6代替实施例21中的磷腈鎓盐化合物氯化{四[三(二甲氨基)正膦亚基氨基]鏻}外,用实施例21中相同的方式进行反应和定量分析。在30分钟后、1小时后、3小时后和6小时后对-氟硝基苯的产率分别为5%、11%、23%和34%。
实施例22
除了用对-氟硝基苯代替实施例21中的对-氯代硝基苯及用苯酚钠盐代替实施例21中的氟化钾外,用与实施例21完全相同的方式进行反应。此外反应温度改变为80℃及反应时间改变为3小时且未在中途跟踪反应。生成目标化合物4-苯氧基硝基苯的产率为98%。
实施例23
除了用六溴苯代替实施例21中的对-氯代硝基苯、改变所使用氟化钾的数量为摩尔数的3倍及用1,3-二甲基-2-咪唑啉酮代替DMSO外,用与实施例21完全相同的方式进行反应。此外,反应温度改变为200℃及反应时间改变为9小时且未在中途跟踪反应。生成目标化合物1,3,5-三氟-2,4,6-三溴苯的产率为85%。
实施例24
除了用三[三(二甲氨基)正膦亚基氨基](二甲氨基)鏻乙醇盐[(Me2N)3P=N]3P+(NMe2)C2H5O-代替实施例1中的四[三(二甲氨基)正膦亚基氨基]鏻甲醇盐外,用与实施例1完全相同的方式进行反应。目标化合物苯乙醚生成的产率为66%。
工业适用性
根据本发明方法,可在比常规方法更温和的条件下进行卤代芳香化合物特别是易工业生产和易得到的氯代芳香化合物的亲核取代反应,并以高的产率生产目标取代芳香化合物。
Claims (17)
1.被Q取代的取代芳香化合物的一种制备方法,它包括:
由化学式(1)表示的磷腈鎓盐化合物:
在化学式中:
Q-表示由无机酸或活泼氢化合物消去一个质子而衍生的阴离子,该活泼氢化合物具有在氧原子、氮原子或硫原子上的活泼氢;
a、b、c和d各独立地为0或1,但它们不能同时全部是0;及
R基团表示相同或不同的C1-10烷基或C1-4烷基苯基,或在一个共同氮原子上的两个R基团连接在一起形成C4-6亚烷基;与具有卤素原子的卤代芳香化合物反应,其中的芳香化合物为任选取代的苯,萘或含有1-2个N,O或S的芳香杂环化合物;由此,在卤代芳香化合物中至少一个卤素原子被Q取代,这里Q表示化学式(1)中的Q-消去一个电子而衍生的无机基团或有机基团。
3.根据权利要求1的一种方法,其中a、b、c和d中至少三个是1。
4.根据权利要求2的一种方法,其中a、b、c和d中至少三个是1。
5.根据权利要求1的一种方法,其中全部R基团是相同或不同的具有1~10个碳原子的烷基。
6.根据权利要求2的一种方法,其中全部R基团是相同或不同的具有1~10个碳原子的烷基。
7.根据权利要求5的一种方法,其中全部R基团是甲基。
8.根据权利要求6的一种方法,其中全部R基团是甲基。
9.根据权利要求1的一种方法,其中在至少部分R基团之中,在相同氮原子上的两个R基团相互连接形成环状结构;两个R基团连接形成的二价取代基是1,4-亚丁基或1,5-亚戊基。
10.根据权利要求2的一种方法,其中在至少部分R基团之中,在相同氮原子上的两个R基团相互连接形成环状结构;两个R基团连接形成的二价取代基是1,4-亚丁基或1,5-亚戊基。
11.根据权利要求1的一种方法,其中衍生化学式(1)中Q-的化合物是一种卤化氢、氢氰酸、硫氰酸、水、具有1~20个碳原子的羧酸、具有1~20个碳原子的醇、具有6~20个碳原子和1~3个羟基的芳香族化合物、具有2~20个碳原子的脂肪族或芳香族仲胺、单价硫醇和芳香族巯基化合物。
12.根据权利要求2的一种方法,其中衍生化学式(1)中Q-和MQn中Q的化合物是一种卤化氢、氢氰酸、硫氰酸、水、具有1~20个碳原子的羧酸、具有1~20个碳原子的醇、具有6~20个碳原子和1~3个羟基的芳香族化合物、具有2~20个碳原子的脂肪族或芳香族仲胺、单价硫醇和芳香族巯基化合物。
13.根据权利要求1的一种方法,其中当化学式(1)中的Q-不是F-时,该卤代芳香化合物是不活泼的氟代芳香族烃类化合物、不活泼的氯代芳香族烃类化合物、不活泼的溴代芳香族烃化合物、活泼的氟代芳香族烃类化合物、活泼的氯代芳香族烃类化合物、活泼的溴代芳香族烃类化合物、氯代芳香族杂环化合物或溴代芳香族杂环化合物,其中的芳香族烃类化合物为任选取代的苯或萘,而芳香杂环化合物为任选取代的含有1-2个N,O或S的芳香杂环化合物。
14.根据权利要求2的一种方法,其中当化学式(1)中的Q-和MQn中的Q分别不是F-和F时,该卤代芳香化合物是不活泼的氟代芳香族烃类化合物、不活泼的氯代芳香族烃类化合物、不活泼的溴代芳香族烃化合物、活泼的氟代芳香族烃类化合物、活泼的氯代芳香族烃类化合物、活泼的溴代芳香族烃类化合物、氯代芳香族杂环化合物或溴代芳香族杂环化合物,其中的芳香族烃类化合物为任选取代的苯或萘,而芳香杂环化合物为任选取代的含有1-2个N,O或S的芳香杂环化合物。
15.根据权利要求1的一种方法,其中当化学式(1)中的Q-是F-时,该卤代芳香化合物是不活泼的氯代芳香族烃类化合物、不活泼的溴代芳香族烃类化合物、活泼的氯代芳香族烃类化合物、活泼的溴代芳香族烃类化合物、氯代芳香族杂环化合物或溴代芳香族杂环化合物,其中的芳香族烃类化合物为任选取代的苯或萘,而芳香杂环化合物为任选取代的含有1-2个N,O或S的芳香杂环化合物。
16.根据权利要求2的一种方法,其中当化学式(1)中的Q-和MQn中的Q分别是F-和F时,该卤代芳香化合物是不活泼的氯代芳香族烃类化合物、不活泼的溴代芳香族烃类化合物、活泼的氯代芳香族烃类化合物、活泼的溴代芳香族烃类化合物、氯代芳香族杂环化合物或溴代芳香族杂环化合物,其中的芳香族烃类化合物为任选取代的苯或萘,而芳香杂环化合物为任选取代的含有1-2个N,O或S的芳香杂环化合物。
17.根据权利要求2的一种方法,其中MQn中的M是一种碱金属原子。
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