Heterocyclic compound preparing
    41.
    发明授权
    Heterocyclic compound preparing 有权
    杂环化合物制备

    公开(公告)号:US09447064B2

    公开(公告)日:2016-09-20

    申请号:US14266342

    申请日:2014-04-30

    发明人: Chun Yu Ho

    摘要: Disclosed is a process for selectively producing (D+1)-member heterocyclic compounds from corresponding unactivated dienes or derivatives thereof in the presence of a transition metal or lanthanide catalyst or a precursor thereof, relative to D-member heterocyclic rings.

    摘要翻译: 公开了在过渡金属或镧系元素催化剂或其前体相对于D族杂环的存在下,从相应的未活化的二烯或其衍生物中选择性地生产(D + 1) - 元素杂环化合物的方法。

    Process for the preparation of novel stabilized phosphorus ylides
    43.
    发明授权
    Process for the preparation of novel stabilized phosphorus ylides 失效
    制备新型稳定化磷内鎓盐的方法

    公开(公告)号:US5856558A

    公开(公告)日:1999-01-05

    申请号:US912799

    申请日:1997-08-18

    CPC分类号: C07F9/60 C07F9/5352 G03C1/10

    摘要: The present invention relates to novel stabilized phosphorous ylides and processes for their preparation. More particularly, the present invention relates to a process for substituting the carbonyl oxygen of 2-formyl- or 2-oxoalkylidenetriphenyl-phosphoranes (OATP) by other stabilizing groups to form novel compounds having an increased tendency to form complexes or compounds which absorb in the visible region of the spectrum.The compounds according to the present invention areCompounds of the formula (1)Ph.sub.3 .dbd.CH--C(R).dbd.Nu (1)wherein R is hydrogen, a C.sub.1 -C.sub.5 -alkyl, C.sub.1 -C.sub.3 -fluoroalkyl or perfluoroalkyl radical, an unfluorinated or fluorinated C.sub.6 -C.sub.14 -aryl radical or a group OCH.sub.3 ; andNu is S, Se, C(CN).sub.2, NH, PhN, PhNHN, ##STR1## or a radical of the formulae (a), (b), (c), (d) or (e) ##STR2## wherein Z is C(CH.sub.3).sub.2, S or N(CH.sub.3) and n=1 or 2 (provided that the combinations R.dbd.Ar, SAlk or OAlk and Nu.dbd.NPh, and the combinations R.dbd.H, Alk or aryl and Nu.dbd.S are excluded) are disclosed, as well as methods for making them.

    摘要翻译: 本发明涉及新的稳定磷叶内鎓及其制备方法。 更具体地说,本发明涉及用其它稳定基团取代2-甲酰基或2-氧代亚烷基三亚膦基(OATP)的羰基氧的方法,形成具有增加倾向于形成复合物或化合物的化合物的新型化合物 可见光谱区域。 根据本发明的化合物是式(1)的化合物,Ph 3 = CH-C(R)= Nu(1)其中R是氢,C 1 -C 5 - 烷基,C 1 -C 3 - 氟烷基或全氟烷基, 未氟化或氟化的C 6 -C 14 - 芳基或基团OCH 3; 和Nu是S,Se,C(CN)2,NH,PhN,PhNHN,IMA或者式(a),(b),(c),(d)或(e) (a)(b)(c)(d)和n = 1或2(条件是组合R = Ar,SAlk或OAlk和Nu = NPh,组合R = H ,Alk或芳基和Nu = S被排除),以及制备它们的方法。

    Preparation and use of (2-butene-1,4-diyl) magnesium complexes in
organic synthesis
    45.
    发明授权
    Preparation and use of (2-butene-1,4-diyl) magnesium complexes in organic synthesis 失效
    (2-丁烯-1,4-二基)镁配合物在有机合成中的制备与应用

    公开(公告)号:US5581004A

    公开(公告)日:1996-12-03

    申请号:US323601

    申请日:1994-10-17

    申请人: Reuben D. Rieke

    发明人: Reuben D. Rieke

    摘要: The magnesium complexes of cyclic hydrocarbons and conjugated dienes, such as 1,2-dimethylenecycloalkanes and 1,3-butadienes, are readily prepared in high yields using highly reactive magnesium. Reactions of these (2-butene-1,4-diyl)magnesium reagents with electrophiles such as dibromoalkanes, alkylditosylates, alkylditriflates, bromoalkylnitriles, esters, or amides serve as a convenient method for synthesizing carbocyclic systems. Significantly, carbocycles prepared by this method contain functional groups such as the exocyclic double bond or a keto group in one of the rings which could be used for further elaboration of these molecules. Furthermore, fused bicyclic systems containing a substituted five-membered ring can be conveniently prepared at high temperatures by the reactions of (2-butene-1,4-diyl)magnesium complexes with carboxylic esters or acid halides whereas low temperatures lead to regioselective synthesis of .beta.,.gamma.-unsaturated ketones. Additionally, .gamma.-lactones, including spiro .gamma.-lactones, can be easily prepared in a one pot synthesis from the reaction of (2-butene-1,4-diyl)magnesium complexes with a ketone or aldehyde and carbon dioxide.

    摘要翻译: 环状烃和共轭二烯的镁络合物如1,2-二甲基环己烷和1,3-丁二烯以高产率容易地用高活性镁制备。 这些(2-丁烯-1,4-二基)镁试剂与亲电试剂例如二溴烷烃,烷基二羧酸酯,烷基三磷酸酯,溴代烷基腈,酯或酰胺的反应作为合成碳环体系的方便方法。 显着地,通过该方法制备的碳环在其中一个环中含有诸如环外双键或酮基的官能团,其可用于进一步制备这些分子。 此外,含有取代的五元环的稠合双环系统可以通过(2-丁烯-1,4-二基)镁配合物与羧酸酯或酰基卤的反应在高温下方便地制备,而低温导致区域选择性合成 β,γ-不饱和酮。 另外,可以通过(2-丁烯-1,4-二基)镁配合物与酮或醛和二氧化碳的反应,在一锅合成中容易地制备γ-内酯,包括螺γ-内酯。

    Preparation and use of (2-butene-1,4-diyl)magnesium complexes in organic
synthesis
    47.
    发明授权
    Preparation and use of (2-butene-1,4-diyl)magnesium complexes in organic synthesis 失效
    (2-丁烯-1,4-二基)镁配合物在有机合成中的制备与应用

    公开(公告)号:US5498734A

    公开(公告)日:1996-03-12

    申请号:US100058

    申请日:1993-07-30

    申请人: Reuben D. Rieke

    发明人: Reuben D. Rieke

    摘要: The magnesium complexes of cyclic hydrocarbons containing conjugated dienes, such as 1,2-dimethylenecycloalkanes, and 1,3-butadienes, are readily prepared in high yields using highly reactive magnesium. Reactions of these (2-butene-1,4 diyl)magnesium reagents with electrophiles such as dibromoalkanes, alkylditosylates, alkylditriflates, bromoalkylnitriles, esters, or amides serve as a convenient method for synthesizing carbocyclic systems. Significantly, carbocycles prepared by this method contain functional groups such as the exocyclic double bond or a keto group in one of the rings which could be used for further elaboration of these molecules. Furthermore, fused bicyclic systems containing a substituted five-membered ring can be conveniently prepared at high temperatures by the reactions of (2-butene-1,4-diyl)magnesium complexes with carboxylic esters or acid halides whereas low temperatures lead to regioselective synthesis of .beta.,.gamma.-unsaturated ketones. Additionally, .gamma.-lactones, including spiro .gamma.-lactones, can be easily prepared in a one pot synthesis from the reaction of (2-butene-1,4-diyl)magnesium complexes with a ketone or aldehyde and carbon dioxide. Also, .delta.-lactones can be easily prepared in a one pot synthesis from the reaction of (2-butene-1,4-diyl)magnesium complexes with epoxides followed by reaction with CO.sub.2. Use of .alpha.-hydroxy epoxides without the addition of CO.sub.2 leads to the synthesis of vicinal diols. Chiral epoxides lead to chiral alcohols.

    摘要翻译: 使用高反应性镁容易地以高产率制备含有共轭二烯的环状烃如1,2-二甲基环己烷和1,3-丁二烯的镁络合物。 这些(2-丁烯-1,4-二基)镁试剂与亲电试剂如二溴烷烃,烷基二羧酸酯,烷基三氟甲磺酸酯,溴代烷基腈,酯或酰胺的反应作为合成碳环体系的方便方法。 显着地,通过该方法制备的碳环在其中一个环中含有诸如环外双键或酮基的官能团,其可用于进一步制备这些分子。 此外,含有取代的五元环的稠合双环系统可以通过(2-丁烯-1,4-二基)镁配合物与羧酸酯或酰基卤的反应在高温下方便地制备,而低温导致区域选择性合成 β,γ-不饱和酮。 另外,可以通过(2-丁烯-1,4-二基)镁配合物与酮或醛和二氧化碳的反应,在一锅合成中容易地制备γ-内酯,包括螺γ-内酯。 此外,可以通过(2-丁烯-1,4-二基)镁配合物与环氧化物的反应,然后与CO 2反应,在一锅合成中容易地制备δ-内酯。 不加二氧化碳的α-羟基环氧化物的使用导致连位二醇的合成。 手性环氧化物导致手性醇。