CN1198157A - 用作对映体选择性环氧化催化剂的二萘并氮杂䓬鎓盐 - Google Patents
用作对映体选择性环氧化催化剂的二萘并氮杂䓬鎓盐 Download PDFInfo
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- C—CHEMISTRY; METALLURGY
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- C07D301/02—Synthesis of the oxirane ring
- C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
- C07D301/12—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with hydrogen peroxide or inorganic peroxides or peracids
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B53/00—Asymmetric syntheses
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D223/00—Heterocyclic compounds containing seven-membered rings having one nitrogen atom as the only ring hetero atom
- C07D223/14—Heterocyclic compounds containing seven-membered rings having one nitrogen atom as the only ring hetero atom condensed with carbocyclic rings or ring systems
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
- Nitrogen Condensed Heterocyclic Rings (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Plural Heterocyclic Compounds (AREA)
- Epoxy Compounds (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Abstract
式(Ⅰa)或(Ⅰb)化合物,其中A和B每个独立地表示氢或一个,两个或三个亚萘基的取代基,这些取代基选自C<sub>1-6</sub>烷基,C<sub>1-6</sub>烷氧基,芳基,芳氧基,甲硅烷基和甲硅烷氧基;R<sup>1</sup>表示苯基,C<sub>1-6</sub>烷基,苯基C<sub>1-6</sub>烷基或式(a):其中R<sup>2</sup>表示C<sub>1-6</sub>烷基,苯基或苄基,R<sup>3</sup>表示H或OR<sup>4</sup>,其中R<sup>4</sup>是C<sub>1-6</sub>烷基或C<sub>1-6</sub>烷基甲硅烷基;n是0,或整数1或2;以及X<sup>-</sup>是对立离子;制备上述化合物的方法以及该化合物用于对映体选择性地环氧化前手性烯类化合物的用途。
Description
本发明涉及新的化合物及这种化合物作为氧转移反应催化剂的用途。
目前,使用手性催化剂,特别是Jacobsen等人的Salen锰铬合物(国际专利申请,公开号WO/91/14694)的烯类化合物催化不对称环氧化反应,是不对称合成中已确立的方法。这种催化体系的重要性主要是由于不对称环氧化反应本身用途的多样性,这种多样性是由于许多及各种各样的亲核试剂,该亲核试剂能够用于使环氧化物开环,并且提供伴随的不同范围的富对映体产品。该对映体纯产品在用于制造生物学上重要的化合物如杀虫剂,除草剂和药物方面有着越来越多的需求。
除了有机-过渡金属基催化剂如Jacobsen催化剂以外,纯的有机不对称催化剂是公知的。Hanquet等人(Tetrahedron Letters Vol.34,no.45,pp7271-7274)证明,氧杂吖丙啶鎓盐(oxaziridinium)(1S,2R,3R,4S)-N-甲基-1,2-氧桥-3-甲基-4-苯基-1,2,3,4-四氢异喹啉鎓四氟硼酸盐催化反式芪的不对称环氧化反应,并且催化甲基对甲苯基硫化物不对称氧化为相应的亚砜。上述氧杂吖丙啶鎓盐从催化量的亚铵盐和过硫酸氢钾制剂就地制备(Hanquet等人,C.R.Acad Sci.,Paris,1991,313,SII,pp625-628)。
和Salen锰铬合物及其它有机-过渡金属基催化剂不同,氧杂吖丙啶鎓盐催化剂不是通过自由基中间体起作用,因之它们可以广泛用于各种烯类底物,这是因为不需要在烯类(分子)中有π-稳定基(稳定初生的自由基),同时氧杂吖丙啶鎓盐催化剂的氧化反应是立体有择的,即顺式烯得到顺式环氧化物;反式烯得到反式环氧化物。虽然有这些优点,但是至今氧杂吖丙啶鎓盐催化剂还没有在工业规模上用于氧化体系。
目前故经发现,一系列新的氧杂吖丙啶鎓盐在烯类化合物的催化不对称环氧化反应中显示了更大的希望。所使用的催化反应是简单的,并且完全可以使用容易得到的廉价的试剂及对环境安全的溶剂。
因此,本发明首先提供式(Ia)或(Ib)的化合物:其中A和B各自独立地表示氢或一个,二个或三个亚萘基的取代基,这些取代基选自C1-6烷基,C1-6烷氧基,芳基,芳氧基,甲硅烷基和甲硅烷氧基;R1表示苯基,C1-6烷基,苯基C1-6烷基或下式(a)其中R2表示C1-6烷基,苯基或苄基,R3表示H或OR4,其中R4是C1-6烷基或C1-6烷基甲硅烷基,n是0或1或2的整数;和X是对立离子。
合适的A是氢。
合适的B是氢。
当R1表示C1-6烷基时,其实例是甲基和乙基。
R1的实例是苄基。
合适的R2是C1-6烷基。
合适的R3是C1-6烷基。
优选R1表示C1-6烷基。
对立离子X-的含义包括BF4 -,Cl-,Br-,I-,ClO4 -和PF6 -;
优选对立离子X-为BF4 -。
合适的芳基A是苯基。
在本文中,烷基无论是单独存在或者作为其它基团如烷氧基或芳烷基的一部分,均为直链或支链的含有1-6个碳原子的烷基,如甲基,乙基,正丙基,异丙基,正丁基,异丁基或叔丁基。
R1-L1 (III)其中R1定义如式(I)中的定义,L1是离去基或原子,然后用含对立离子X-的原料使所得到的化合物成盐。L1通常表示卤化物如溴化物或碘化物,甲苯磺酰基或甲磺酰基。
式(II)和(III)化合物之间的反应可以在有或无溶剂存在下进行,当使用溶剂时,通常为有机溶剂,一般是惰性有机溶剂如二氯甲烷;反应于低温到升温下进行,如0°-100℃的范围内,通常在室温下进行;优选反应在无水条件下进行;并且优选反应在惰性气体例如氮气保护下进行。
使用含对立离子X-的原料的成盐反应采用任何常规方法完成,但通常于反应使用的溶剂中及室温下进行。
含对立离子X-的原料可以是任何常规的原料,例如适当的金属盐,特别是银盐,但是通常烷基化试剂(III)也是对立离子X-的原料。例如当制备其中R1是C1-6烷基和X-是BF4 -的式(Ia)或(Ib)化合物时,式(II)化合物是其中R1a为C1-6烷基,特别是甲基的化合物(R1a)3OBF4。
式(IIa)和(IIb)化合物可以通过氧化式(IV)的手性胺来制备:其中A和B如同式(I)中的定义,反应使用高锰酸钾作氧化剂,按照Fleischhacker等人所述方法进行(monatsh Chem.1989 120765)。
式(IV)的手性化合物可以从式(IV)的外消旋化合物通过常规的拆分方法制备,例如Hawkins和Fu所述的方法(Organic Chemistry1986,51,2820-2822)。
式(III)化合物是已知化合物,或者可以采用制备已知化合物使用的类似方法来制备,例如W.S.Johnson等人所述的方法(Journal ofAmerican Chemical Society,1963,85,1409)。
式(IV)化合物是已知化合物,或者可以采用制备已知化合物使用的类似方法来制备,例如Hawkins和Fu所述的方法(文献同上)。
如果适当,其中R1表示上述定义的式(a)的式(Ia)和(Ib)化合物可以通过环化式(Va)或(Vb)化合物制备:其中A,B,R2,R3和n的定义如式(I)中的定义,L2为离去基,其后用含对立离子X-的原料使所得化合物成盐。
式(Va)和(Vb)化合物的环化反应在适当的有机溶剂中进行。通常为非质子传递溶剂如丙酮,反应在室温或升温下进行,通常为溶剂的回流温度。
含对立离子X-的原料的成盐反应使用任何常规方法进行,但通常在环化反应使用的溶剂中于室温下进行。含对立离子X-的原料可以是任何常规的原料,如适当的金属盐,例如当X-是BF4-时,合适的原料是碱金属四氟硼酸盐如四氟硼酸钠或四氟硼酸银。
式(VIa)或(VIb)化合物和式(VII)化合物之间的反应可以用任何合适的有机溶剂进行,通常是非质子传递溶剂如四氢呋喃,反应通常在低温或中等升温例如-78-50℃范围内进行。
式(VII)化合物是已知化合物,或者它们可用制备已知化合物使用的类似方法制备,例如Evans等人所述的方法(Organic Synthesis,Vol 68,1989,77)
式(VIa)和(VIb)化合物可以按照下述方法制备:其中A和B的定义如式(I)中的定义,第1步-第4步的反应条件及所用试剂见下述参考文献:第1步和第2步:N.Naigrot,J.P.Mazaleyrat,Synthesis,1985,
p 317;第3步:H.B.Hass,M.L.Bender,Org.Syn.Coll.Vol.
4,1963,932;第4步:B.Bezas,L.Zervas,JACS,1961,83,719。
如上所述,式(I)化合物用作烯类化合物不对称环氧化反应的催化剂。因此本发明的另一方面是提供对映体选择性地环氧化前手性烯类的方法,例如1-苯基环己烯,1-甲基环己烯,反式芪和甲基芪。上述方法包括在催化剂存在下使前手性烯类化合物和亲核性的氧化剂反应,其特征是上述催化剂是式(Ia)或(Ib)化合物:其中A和B每个独立地表示氢或一个,两个或三个亚萘基的取代基,这些取代基选自C1-6烷基,C1-6烷氧基,芳基,芳氧基,甲硅烷基,甲硅烷氧基;R1表示苯基,C1-6烷基,苯基C1-6烷基或式(a)的基团:其中R2表示C1-6烷基,苯基或苄基;R3表示H或OR4,其中R4是C1-6烷基或C1-6烷基甲硅烷基及n是0或整数1或2;以及X是对立离子。
一个合适的亲核氧化剂是过硫酸氢钾制剂(KHSO5)和NaHCO3的混合物。
环氧化反应可以使用任何适当的方法进行,其中使前手性烯烃,亲核氧化剂和式(Ia)或(Ib)化合物反应得到所需的环氧化物。
反应在有机溶剂如乙腈,二甲亚砜,二甲基甲酰胺或吡啶,或者在有机溶剂/水的混合物如含水乙腈中进行。
当采用过硫酸氢钾制剂/NaHCO3作亲核氧化剂时,含水乙腈是特别合适的反应溶剂。
反应在低温到中等升温下,如-20到50℃范围内,优选在室温下进行。
反应适宜在中性或碱性pH下如pH7-14范围内进行,优选在pH8-10范围内进行。
式(Ia)或(Ib)化合物对前手性烯烃的合适的摩尔比是1-20摩尔%,优选范围是5-10摩尔%。
下述制备和实施例用以说明本发明。
亚铵盐催化剂一般的制备方法:
将相应的烷基化剂加入到所需亚铵的CH2Cl2溶液中,反应于室温下进行直到完成,除去溶剂,在乙醚中沉淀出残留物,得到所需的盐。实施例1:(S-(+)-5,5-二氢-2H-二萘并〔2,1-C:1′,2′-e〕-N-甲基氮杂四氟硼酸盐
于氮气保护下,一次性地将Me3OBF4(222mg,1.5mmol)加入到由制剂1的(S)-亚胺(400mg,1.36mmol)的无水CH2Cl2(10ml)溶液中,于N2保护下室温反应24小时,除去溶剂,在乙醚中沉淀出残留物,得到所需的盐(518mg,96%)
[α]D 20+1070(c1.1 in CH2Cl2);δH(250MHz;CDCl3)4.05(3H,s,CH3),4.6(1H,d,J 12.5Hz,ArCH′H),4.95(1H,d,J12.5Hz,ArCHH′),7.0-8.25(12H,m,Ar-H),和9.2(1H,s,CH=N);δC(62MHz;CDCl3)48.76,58.8,125.29,126.14,126.78,126.9,127.12,127.21,127.5,128.68,129.54,129.67,130.12,130.89,131.41,131.78,131.93,133.87,135.29,141.12,和168.36;m/z(FAB)308(M+-87,100%)(测定值308.1448.C23H18N计算值308.1439).实施例2:(S)-(+)-5,5-二氢-2H-二萘并〔2,1-C:1′,2′-e〕-N-甲基氮杂碘化物
制剂1的(S)-亚胺(50mg,0.17mmol)的碘甲烷(2ml)溶液于室温下搅拌,很快在反应混合物中形成黄色固体,24小时后反应物的TLC表明仅有少量的原料残留。用乙醚研制除去剩余的亚胺和过量碘甲烷,于高真空下干燥后得到所需的化合物,是黄色固体(72mg,97%),δH(250MHz;CDCl3)4.25(3H,s,CH3),4.70(1H,d,J 13.1Hz,ArCH′H),4.85(1H,d,J 13.1Hz,ArCHH′),7.00-8.50(12H,m,Ar-H),和10.50(1H,s,N=CH).实施例3:(S)-(+)-5,5-二氢-2H-二萘并〔2,1-C:1′,2′-e〕-N-甲基氮杂高氯酸盐
将AgClO4(34.3mg,0.17mmol)的丙酮(1ml)溶液加入到实施例2得到的(S)-亚铵盐(72mg,0.16mmol)的CH2Cl2(1ml)溶液中,过滤出形成的固体,浓缩滤液,从乙醚中沉淀,得到所需的亚铵盐。于高真空下干燥,得到所需化合物,为黄色固体,(60mg,90%)。[α]D 20+769(c 1.09在丙酮中);δH(250MHz;CDCl3)4.15(3H,s,CH3),4.70(1H,d,J 13Hz,ArCH′H),4.80(1H,d,J 13Hz,ArCHH′),7.0-8.2(12H,m,Ar-H),和9.35(1H,s,N=CH);δC(100MHz;d6-丙酮)49.44,59.19,126.59,126.64,127.62,127.85,127.93,128.03,128.46,129.58,129.60,130.01,130.24,130.26,130.91,131.76,132.18,132.40,132.82,134.83,136.92,141.86,和169.98.实施例4:(R)-(-)-5,5-二氢-2H-二萘并〔2,1-C:1′,2′-e〕-N-甲基氮杂六氟磷酸盐
将AgPF6(40.7mg,0.16mmol)的丙酮(1ml)溶液加入到实施例2得到的(R)-亚铵盐(70mg,0.16mmol)的CH2Cl2(2ml)溶液中,过滤出形成的固体,浓缩滤液,从乙醚中沉淀,得到所需的亚铵盐,于高真空下干燥后得到所需的化合物,为黄色固体,(65mg,92%)。[α]D 20-778(c1.25在丙酮中);δH(250MHz;CDCl3)4.09(3H,s,CH3),4.64(1H,d,J 13Hz,ArCH′H),4.89(1H,d,J 13Hz,ArCHH′),7.00-8.25(12H,m,Ar-H),和9.12(1H,s,N=CH);δC(100MHz;CD2Cl2)49.22,59.60,125.17,125.95,126.67,127.42,127.52,127.82,128.18,129.02,129.07,129.96,130.24,130.97,131.42,131.94,32.37,132.44,134.37,135.02,135.92,142.19,和168.56.实施例5:(S)-(+)-5,5-二氢-2H-二萘并〔2,1-C:1′,2′-e〕-N-甲基氮杂碘化物
将制剂1的(S)-亚胺(50mg,0.17mmol)的碘乙烷(2ml)溶液于室温下搅拌,立即在反应混合物中形成黄色固体,24小时后TLC表明仅有少量原料残留。用乙醚研制除去残留的亚胺和过量的碘乙烷,高真空干燥后得到所需的产品,为黄色固体(60mg,98%),mp>200°(分解)。[α]D 20+878(c0.41 in CH2Cl2);δH(250MHz;CDCl3)1.51(3H,t,J 7Hz,CH3),4.45-4.75(2H,m,CH2CH3),4.6(1H,d,J,12.5Hz,ArCH′H),4.95(1H,d,J 12.5Hz,ArCHH′),7.00-8.60(12H,m,Ar-H),和10.60(1H,s,N=CH);δC(100MHz;CD2Cl2)14.30,57.75,57.86,125.21,127.09,127.42,127.62,127.68,127.89,128.93,129.04,129.75,129.84,130.62,131.72,131.93,132.04,132.45,134.23,135.41,135.80,141.95,和168.23;m/z(FAB)323(M+-128),322(M+-129,100%),和308(M+-141);HRMS:m/z计算值322.1604.C24H20N(M+-127)测定值322.1596.实施例6:(R)-(-)-5,5-二氢-2H-二萘并〔2,1-C:1′,2′-e〕-N-乙基氮杂四氟硼酸盐
将AgBF4(40mg,0.2mmol)的丙酮(1ml)溶液加入到实施例5得到的(R)-亚铵盐(76mg,0.17mmol)的CH2Cl2(2ml)溶液中,过滤除去形成的固体(AgI),浓缩滤液得到的泡沫用乙醚研制,得到所需产物,为黄色胶状物(59mg,84%)。
[α]D 20-832(c0.87在丙酮中);δH(250MHz;CD2Cl2)1.50(3H,t,J 6.5Hz,CH3),4.25(2H,q,J 6.5Hz,CH2CH3),4.53(1H,d,J 13Hz,ArCH′H),4.94(1H,d,J 13Hz,ArCHH′),6.9-8.15(12H,m,Ar-H),和9.13(1H,s,N=CH);δC(100MHz:CD2Cl2)13.87,57.49,58.38,125.46,126.33,126.88,127.02,127.10,127.15,127.86,128.86,128.97,129.67,129.97,130.64,131.60,131.87,132.01,132.40,134.25,135.82,141.86,和167.90实施例7:(S)-(+)-5,5-二氢-2H-二萘并〔2,1-C:1′,2′-e〕-N-苄基-氮杂溴化物
制剂1的(S)-亚胺(50mg,0.17mmol)的苄基溴(2ml)溶液于室温搅拌2天,反应物TLC表明有少量原料残留。真空下除去过量的苄基溴,用乙醚研制残留物以除去未反应的原料及残留的苄基溴,高真空干燥后得到所需的化合物,为黄色固体(75mg,95%),mp 150-152℃(分解)。[α]D 20+450(c1.48 in CH2Cl2);δH(250MHz;CDCl3)4.45(1H,d,J 13.4Hz,ArCH′H),4.90(1H,d,J 13.4Hz,ArCHH′),5.80(1H,d,J,13.0Hz,PhCH′H),5.94(1H,d,J 13.0Hz,PhCHH′),6.75-8.6(17H,m,Ar-H),和11.22(1H,s,N=CH);δC(100MHz;CDCl3)56.55,65.28,124.68,126.86,126.94,127.19,127.44,128.47,128.65,128.74,128.97,129.35,129.49,129.87,130.19,130.90,131.03,131.45,131.60,133.44,135.34,141.42,和169.45;m/z(FAB)385(M+-79),384(M+-80,100%);HRMS:m/z计算值384.1745 C29H22N(M+-80)测定值384.1752.实施例8:(R)-(-)-5,5-二氢-2H-二萘并〔2,1-C:1′,2′-e〕-N-苄基-氮杂四氟硼酸盐
往实施例7得到的(R)-溴化物盐(从50mg,0.17mmol制剂1的(R)-亚胺制备)的CH2Cl2(2ml)溶液中加入AgBF4(40mg,0.2mmol),分离形成的固体(AgBr),浓缩滤液,用乙醚研制所得泡沫,得到所需产品,为黄色胶状物(48mg,60%)。
[α]D 20-637(c0.6在丙酮中);δH(250
MHz;CDCl3)4.55(1H,d,J 12.5Hz,ArCH′H),4.95(1H,d,J 12.5Hz,
ArCHH′),5.48(1H,d,J 14Hz,PhCH′H),5.58(1H,d,J 13Hz,PhCHH′),6.65-
8.16(17H,m,Ar-H),和9.55(1H,s,N=CH);δC(100MHz;CDCl3)56.54,
66.12,124.71,126.60,126.63,126.92,127.14,127.51,128.50,128.66,129.43,
129.47,129.70,130.01,130.18,130.29,130.64,130.95,131.05,131.45,131.60,
133.46,135.41,135.44,141.56,和168.17.
使用亚铵盐催化剂的催化环氧化反应一般方法
往烯类化合物(0.5mmol)于乙腈(4.5ml)和水(1-2滴)的混合物的溶液中先加入精细粉碎的NaHCO3(2mmol)和过硫酸氢钾制剂(0.5mmol),然后加入催化剂(0.05mmol或0.025mmol)。将所得黄色悬浮液于室温及良好搅拌情况下反应,用薄层色谱法(TLC)监测反应,通常反应完成时混合物的颜色由亮黄色变为接近无色。往反应混合物中加水,再用二氯甲烷萃取。合并有机萃取液,用无水硫酸钠干燥,用旋转蒸发器浓缩,将所得产物用柱色谱法提纯,得到所需的环氧化物。实施例1 苯基环己烯氧化物的制备
往苯基环己烯(79mg,0.5mmol)于乙腈(4.5ml)和水(2滴)的混合物的溶液中先加入精细粉碎的NaHCO3(168mg,2mmol)和过硫酸氢钾制剂(307mg,0.5mmol),然后再加入催化剂(0.05mmol)。将所得黄色悬浮液于室温及良好搅拌情况下反应。用TLC跟踪反应,指出反应经2小时完成。将水(3ml)加入到反应混合物中,随后萃取到二氯甲烷中。合并有机萃取液,用无水硫酸钠干燥,用旋转蒸发器浓缩,将产物用柱色谱提纯,用2%乙酸乙酯/汽油混合物作洗脱剂,得到所需化合物,为无色油状物(72mg,83%产率,70%e.e)
然后使苯基环己烯环氧化为苯基环己烯氧化物的环氧化反应采用本发明的其它催化剂完成,所得结果列于表1。
表1
实施例 R1 X 产率% ee%
No.
1 Me BF4 83 70
3 Me ClO4 54 74
4 Me PF6 48 61
5 Et I 55 78
6 Et BF4 78 76
7 Bn Br 71 74
8 Bn BF4 78 73制剂1:R(-)和S(+)5,5-二氢-2H-二萘并〔2,1-C:1′,2′-e〕氯杂
往(R)-或(S)-胺(295mg,1mmol)(Journal of OrganicChemistry,1986,51,2820-2822)的THF(5ml)溶液中加入KMnO4(648mg,4mmol)。反应于室温进行5小时,过滤除去固体,浓缩滤液,用柱色谱法提纯,用乙酸乙酯∶汽油(1∶1)作洗脱剂,得所需化合物,为浆状物(234mg,80%)。(S)-异构体,[α]D 20+1363.7,(c 1.19 in CH2Cl2);(R)-异构体,[α]D 20-1363.7,(c 1.19 in CH2Cl2);两种异构体:δH(250MHz;CDCl3)3.95(1H,dd,J 2.2Hz和11Hz,ArCH′H),4.96(1H,d,J 11Hz,ArCHH′),7.0-8.1(12H,m,Ar-H),和8.6(1H,d,J 2.2Hz,CH=N);δC(62MHz;CDCl3)55.90,124.36,125.27,125.87,126.05.126.42,126.69,127.16,127.49,128.07,128.25,128.44,129.18,130.49,131.70,132.08,132.34,132.99,135.04,136.99,140.96,和d 162.47;m/z(FAB)294(M++1,100%),154(M+-139),and 136(M+-157)(测定值294.1275.C22H16N计算值s 294.1283).
Claims (10)
1.式(Ia)或(Ib)的化合物其中A和B独立地代表氢,一个,两个或三个亚萘基的取代基,所述取代基选自C1-6烷基,C1-6烷氧基,芳基,芳氧基,甲硅烷基和甲硅烷氧基;R1代表苯基,C1-6烷基,苯基C1-6烷基或下式(a):其中R2代表C1-6烷基,苯基或苄基;R3代表H或OR4,其中R4是C1-6烷基或C1-6烷基甲硅烷基,和n是0或整数1或2;以及X是对立离子。
2.按照权利要求1的化合物,其中A代表氢和B代表氢。
3.按照权利要求1或2的化合物,其中R1代表C1-6烷基。
4.按照权利要求1-3中的任何一项的化合物,其中R1代表C1-6烷基。
5.按照权利要求1-4中的任何一项的化合物,其中R1代表甲基或乙基。
6.按照权利要求1-5中的任何一项的化合物,其中的对立离子X-是选自BF4 -,Cl-,Br-,I-,ClO4 -和PF6 -。
7.按照权利要求1-6中的任何一项的化合物,其中对立离子X-是BF4-。
8.按照权利要求1的化合物,选自:(S)-(+)-5,5-二氢-2H-二萘并〔2,1-C:1′,2′-e〕-N-甲基氮杂四氟硼酸盐;(S)-(+)-5,5-二氢-2H-二萘并〔2,1-C:1′,2′-e〕-N-甲基氮杂碘化物;(S)-(+)-5,5-二氢-2H-二萘并〔2,1-C:1′,2′-e〕-N-甲基氮杂高氯酸盐;(R)-(-)-5,5-二氢-2H-二萘并〔2,1-C:1′,2′-e〕-N-甲基氮杂六氟磷酸盐;(S)-(+)-5,5-二氢-2H-二萘并〔 2,1-C:1′,2′-e〕-N-乙基氮杂碘化物;(R)-(-)-5,5-二氢-2H-二萘并〔2,1-C:1′,2′-e〕-N-乙基氮杂四氟硼酸盐;(S)-(+)-5,5-二氢-2H-二萘并〔2,1-C:1′,2′-e〕-N-苄基氮杂溴化物;和(R)-(-)-5,5-二氢-2H-二萘并〔2,1-C:1′,2′-e〕-N-苄基氮杂四氟硼酸盐。
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GB (1) | GB9516309D0 (zh) |
HU (1) | HUP9802369A3 (zh) |
IL (2) | IL123136A (zh) |
NO (1) | NO310867B1 (zh) |
NZ (1) | NZ316483A (zh) |
PL (1) | PL186106B1 (zh) |
TR (1) | TR199800190T1 (zh) |
TW (1) | TW330932B (zh) |
WO (1) | WO1997006147A1 (zh) |
ZA (1) | ZA966757B (zh) |
Families Citing this family (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6825160B1 (en) | 1999-08-27 | 2004-11-30 | Procter & Gamble Company | Color safe laundry methods employing cationic formulation components |
US7109156B1 (en) | 1999-08-27 | 2006-09-19 | Procter & Gamble Company | Controlled availability of formulation components, compositions and laundry methods employing same |
US6903060B1 (en) | 1999-08-27 | 2005-06-07 | Procter & Gamble Company | Stable formulation components, compositions and laundry methods employing same |
MXPA02002124A (es) | 1999-08-27 | 2002-09-18 | Procter & Gamble | Componentes de formulacion de incremento de estabilidad y composiciones y metodos de lavanderia que emplean los mismos. |
US6818607B1 (en) | 1999-08-27 | 2004-11-16 | Procter & Gamble Company | Bleach boosting components, compositions and laundry methods |
US6821935B1 (en) | 1999-08-27 | 2004-11-23 | Procter & Gamble Company | Color safe laundry methods employing zwitterionic formulation components |
US7557076B2 (en) | 2002-06-06 | 2009-07-07 | The Procter & Gamble Company | Organic catalyst with enhanced enzyme compatibility |
US7169744B2 (en) | 2002-06-06 | 2007-01-30 | Procter & Gamble Company | Organic catalyst with enhanced solubility |
JP4779109B2 (ja) * | 2004-11-17 | 2011-09-28 | 国立大学法人京都大学 | 軸不斉を有する光学活性アミノ酸誘導体及び該アミノ酸誘導体を不斉触媒として用いる光学活性化合物の製造方法 |
CN101146812B (zh) | 2005-03-03 | 2013-10-16 | 日本曹达株式会社 | 光学活性铵盐化合物、其制造中间体和制造方法 |
AR051659A1 (es) | 2005-06-17 | 2007-01-31 | Procter & Gamble | Una composicion que comprende un catalizador organico con compatibilidada enzimatica mejorada |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5360568A (en) * | 1993-11-12 | 1994-11-01 | Lever Brothers Company, Division Of Conopco, Inc. | Imine quaternary salts as bleach catalysts |
WO1995013352A1 (en) * | 1993-11-12 | 1995-05-18 | Unilever N.V. | Imine quaternary salts as bleach catalysts |
-
1995
- 1995-08-09 GB GBGB9516309.3A patent/GB9516309D0/en active Pending
-
1996
- 1996-07-08 AR ARP960103916A patent/AR003214A1/es not_active Application Discontinuation
- 1996-08-07 US US09/011,010 patent/US6063920A/en not_active Expired - Fee Related
- 1996-08-07 AU AU68723/96A patent/AU6872396A/en not_active Abandoned
- 1996-08-07 CA CA002228902A patent/CA2228902A1/en not_active Abandoned
- 1996-08-07 WO PCT/EP1996/003551 patent/WO1997006147A1/en not_active Application Discontinuation
- 1996-08-07 HU HU9802369A patent/HUP9802369A3/hu unknown
- 1996-08-07 NZ NZ316483A patent/NZ316483A/xx unknown
- 1996-08-07 KR KR1019980700926A patent/KR19990036258A/ko not_active Application Discontinuation
- 1996-08-07 BR BR9609976-3A patent/BR9609976A/pt not_active Application Discontinuation
- 1996-08-07 IL IL12313696A patent/IL123136A/en not_active IP Right Cessation
- 1996-08-07 PL PL96324854A patent/PL186106B1/pl unknown
- 1996-08-07 CZ CZ1998363A patent/CZ292114B6/cs not_active IP Right Cessation
- 1996-08-07 IL IL12313688A patent/IL123136A0/xx unknown
- 1996-08-07 CN CN96197262A patent/CN1098840C/zh not_active Expired - Fee Related
- 1996-08-07 JP JP9508142A patent/JPH11510802A/ja not_active Ceased
- 1996-08-07 EP EP96929238A patent/EP0843664A1/en not_active Withdrawn
- 1996-08-07 TR TR1998/00190T patent/TR199800190T1/xx unknown
- 1996-08-08 ZA ZA9606757A patent/ZA966757B/xx unknown
- 1996-08-09 TW TW085109776A patent/TW330932B/zh active
-
1998
- 1998-02-06 NO NO19980526A patent/NO310867B1/no not_active IP Right Cessation
Also Published As
Publication number | Publication date |
---|---|
JPH11510802A (ja) | 1999-09-21 |
US6063920A (en) | 2000-05-16 |
MX9801064A (es) | 1998-10-31 |
CZ292114B6 (cs) | 2003-08-13 |
AR003214A1 (es) | 1998-07-08 |
TR199800190T1 (xx) | 1998-05-21 |
BR9609976A (pt) | 1999-12-21 |
PL324854A1 (en) | 1998-06-22 |
IL123136A0 (en) | 1998-09-24 |
HUP9802369A3 (en) | 2000-03-28 |
NO310867B1 (no) | 2001-09-10 |
NZ316483A (en) | 1999-05-28 |
KR19990036258A (ko) | 1999-05-25 |
GB9516309D0 (en) | 1995-10-11 |
HUP9802369A2 (hu) | 1999-02-01 |
EP0843664A1 (en) | 1998-05-27 |
TW330932B (en) | 1998-05-01 |
WO1997006147A1 (en) | 1997-02-20 |
AU6872396A (en) | 1997-03-05 |
NO980526L (no) | 1998-02-06 |
PL186106B1 (pl) | 2003-10-31 |
IL123136A (en) | 2001-09-13 |
NO980526D0 (no) | 1998-02-06 |
CZ36398A3 (cs) | 1998-09-16 |
ZA966757B (en) | 1998-02-09 |
CN1098840C (zh) | 2003-01-15 |
CA2228902A1 (en) | 1997-02-20 |
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