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合成了18种内-α-取代-α-甲基双环[2,2,1]庚烷-2-基甲醇(Ⅰ)。测定了所有化合物的折光率(或熔点)、质谱、红外光谱、~1H核磁共振谱、气相色谱的保留时间和薄层色谱的比移值。评定了它们的香气,并与相应的内-α-取代-α-甲基双环[2,2,1]-5-庚烯-2-基甲醇(Ⅱ)系列化合物的香气进行了比较,初步探讨了结构与香气的关系。 相似文献
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以N,N,N′,N′-四甲基联苯二胺、2,6-二甲氧基萘和2,7-二甲氧基萘为光敏剂,在正己烷溶液中实现了双环[2,2,1]-2,5-庚二烯到四环[2,2,1,02,6,03,5]庚烷的异构化。测定了反应的量子产率。讨论了反应机理。通过激发态的光敏剂与二烯之间的电子转移反应,形成单重态和三重态处于平衡状态的离子自由基对中间体。处于溶剂笼中的三重态离子自由基对经电子反传,产生激发三重态二烯。最后该激发态二烯经分子内[2+2]环合加成反应异构化为四环烷。 相似文献
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本文报道用毛细管气相色谱法及毛细管色谱-质谱-计算机体系对蒙古蒿精油化学成分进行分离和鉴定.30个单萜和含氧单萜化合物为2-甲基丁烯-[2]、甲叉环戊烷、7,7-二甲基-3-次甲基-双环(3,1,1)庚烷、α-(艹守)烯、α-蒎烯、莰烯、1-辛烯辛醇-3、β-(艹守)烯、β-蒎烯、α-菲兰烯、冰片烯、对甲基异丙基苯、松油烯醇-[1]、蒿属酮、γ-松油烯、β-松油醇、3,7,7-三甲基-双环(3,1,1)-2-庚醇、α-松油烯、马鞭烯酮、里哪醇、异(艹守)酮、(艹守)酮、樟脑、异胡薄荷酮、异龙脑、松油烯醇-[4]、α-松油醇、香桃木烯醇、反香芹烯醇和顺香芹烯醇. 相似文献
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本文对N-(对-硝基)苄基-1,7,7-三甲基-双环[2.2.1]庚烷-2-亚胺(3)和N-[11—[12-羟基-12-二苯基]甲基]苄基-1,7,7-三甲基-双环[2.2.1]庚烷-2-亚胺(4)进行了X-射线晶体结构分析。采用MOPAC程序的MNDO方法对(+)-樟脑缩苄胺即N-苄基-1,7,7-三甲基-双环[2.2.1]庚烷-2-亚胺(2a)的内部转动势能进行了理论计算。结果表明,(+)-樟脑缩苄胺(2a)以反式(trans)构象形式存在,它在不对称反应中的立体选择性主要受樟脑环上方C10甲基的控制。 相似文献
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报道了7,7-二氯双环[4,1,O]庚烷与某些活性亚甲基化合物阴离子在THF中,经光照得到的产物为单取代物.反应机理涉及SRN1过程. 相似文献
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用双环[2,2,1]庚-5-烯-1,4,5,6,7,7-六氯-2,3-二酸酐与尿素共熔制备双环[2,2,1]庚-5-烯-1,4,5,6,7,7-六氯-2,3-二酰亚胺.此酰亚胺与甲醛和胺(芳香及脂肪胺)在乙醇中反应,可生成N-曼尼希碱,且产率较高.用此法共制备了二十四个N-曼尼希碱,其中二十二个是新化合物.除了11及13号外(见表)都是在室温下获得的.硝基(对、邻)苯胺与甲醛及该酰亚胺的反应,在室温得到双(对、邻硝基苯胺基)甲烷,回馏一小时后亦可获得预期的N-曼尼希碱.先把该酰亚胺转变成N-羟甲基的衍生物,然后再与胺反应也可得到N-曼尼希碱.该酰亚胺与胺-甲醛缩合物反应,不需另加酸同样也生成N-曼尼希碱. 相似文献
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Bösing P Willner A Pape T Hepp A Mitzel NW 《Dalton transactions (Cambridge, England : 2003)》2008,(19):2549-2556
Reactions of bishydroxylamines of the type HON(R)CH2CH2N(R)OH (R=Me, tBu) with trimethyl- and triisopropylgallium gave bicyclic metalla cages of the formula R'2GaO(R)NCH2CH2N(R)OGaR'2 [R'=Me, R=Me (), tBu (); R'=iPr, R=Me (), tBu ()] with six-membered Ga2O2N2-rings. While the complexes show the same core constitution in the solid state, NMR spectra reveal the steric influence of the isopropyl substituent of the compounds / on its behaviour in solution. The reaction of the sterically more demanding substituted tri-tert-butylgallium with HON(Me)CH2CH2N(Me)OH yielded a heterodimeric complex O'-[HON(Me)CH2CH2NH(Me)O(tBu2Ga)]-cyclo-(tBu2Ga)-O,N'-[ON(Me)CH2CH2N(Me)O] () with two gallium atoms of different surrounding and two different bishydroxylamine ligands, one doubly deprotonated and one protonated, but at one end in its tautomeric aminoxide form. Further condensation of was observed to give a tricyclic compound cyclo-[(tBuGa)ON(Me)CH2CH2N(Me)O]2 () with a central Ga2O2N2 ring resulting from two Ga-N donor-acceptor bonds. 相似文献
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Lee TY Wooten AJ Luci JJ Swenson DC Messerle L 《Chemical communications (Cambridge, England)》2005,(43):5444-5446
(C5Me5R)2Ta2Cl4 (d2-d2) disproportionates under dinitrogen to [(C5Me4R)TaCl2]2(mu-N2) and the D3h cluster cation (C5Me4R)3Ta3(mu-Cl)6+ with anionic (C5Me4R)TaCl4-. 相似文献
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[reaction: see text] Additions of vinylic zinc bromide reagents to alpha-chiral aldehydes (R(1) = CH(2)OTBS, R(2) = Me; R(1) = Me, R(2) = OTBS) in the presence of lithiated (+)- or (-)-N-methylephedrine proceed with predominant reagent control to afford anti or syn adducts stereoselectively, except when the aldehydes possess an alkoxy substituent at the alpha- or beta-positions (R(1) = Me, R(2) = OBn; R(1) = CH(2)OBn, R(2) = Me), in which case chelation-controlled adducts predominate. 相似文献
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发现了氯化镍是在双(三甲硅烷基)乙酰胺存在时乙酸烯丙酯与O,O-二烷膦酸酯反应的有用催化剂,反应可在温和条件下以高得率制得烯丙基膦酸酯. 相似文献
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Westenkirchner A Villinger A Karaghiosoff K Wustrack R Michalik D Schulz A 《Inorganic chemistry》2011,50(6):2691-2702
Differently substituted hydrazinophosphanes of the type (Me(3)Si)(2)N-N(SiMe(3))-PR(1)R(2) (R(1) = Cl with R(2) = Me, C(6)F(5) and R(1) = Me, R(2) = C(6)H(5)) have been studied in the reaction with Lewis acids such as ECl(3) (E = Al, Ga). For (Me(3)Si)(2)N-N(SiMe(3))-P(Cl)(Me) and (Me(3)Si)(2)N-N(SiMe(3))-P(Me)(C(6)H(5)), only adduct formation was found while a chlorine/methyl exchange reaction was observed for (Me(3)Si)(2)N-N(SiMe(3))-P(Cl)R (R = C(6)H(5) and C(6)F(5)) leading to the formation of (Me(2)ClSi)(Me(3)Si)N-N(SiMe(3))-P(Me)R, which crystallize as ECl(3) adducts. The free hydrazinophosphanes can be obtained by removal of the Lewis acid with the help of a strong base such as 4-(dimethylamino)pyridine (DMAP). 相似文献
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The syntheses and structures of zirconium and titanium complexes containing the novel chelating trisilane-1,3-diolate ligand [Me2Si(R2SiO)2]2- (R = SiMe3) (5)-H2 are reported. The chloride complexes [Me2Si(R2SiO)2]TiCl2 (7a) and [Me2Si(R2SiO)2]ZrCl2 x 2 THF (7b) were prepared by the reaction of MCl4 (M = Ti, Zr) with [Me2Si(R2SiO)2]2Ti (6a) and [Me2Si(R2SiO)2]2Zr (6b), which are derived from the reaction of 5 with M(NEt2)4, respectively. In the presence of TiCl4, complexes 6a and 7a undergo a ring-opening reaction to produce the dinuclear complex [Me2Si(R2SiO)2][TiCl3]2 (9). [Me2Si(R2SiO)2]TiMe2 (10) and [Me2Si(R2SiO)2]TiBnz2 (11) were prepared in moderate yields from reactions of 7a with 2 equiv of MeMgBr and BnzMgCl, respectively. According to NMR spectroscopic investigations, the reaction of the dimethyltitanium complex 10 with B(C6F5)3 led to full exchange of both methyl groups by C6F5 groups under quantitative formation of [Me2Si(R2SiO)2]Ti(C6F5)2 (12) and a mixture of B(C6F5)(3-n)Me(n), where n = 1-3. The structure of 12 is further evidenced by the preparation of an identical sample from the reaction of 7a with 2 equiv of C6F5MgBr. Refluxing an ether solution of 12 surprisingly gave [Me2Si(R2SiO)2]2TiC6F5]2O (13) as a result of ether cleavage. The structures of the complexes 7a, 7b, 9, 10, and 13 were determined by X-ray crystallography, and structural discussion of the bond parameters will be given. 相似文献
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Factors affecting the coordination mode of an amidato group on aluminum will be presented. The reaction of N-tert-butylalkylacetamide ((t)BuNHCR([double bond]O)) with 1.1 molar equiv of Me(3)Al in refluxing hexane affords a pentacoordinated, dimeric compound [Me(2)Al[eta(2)-(t)BuNC(R)(mu(2)-O)]](2) (3, R = p-(t)Bu-C(6)H(4); 4, R = 2,6-F,F-C(6)H(3); 5, R = Me; 6, R = CF(3); 7, R = p-F(3)C-C(6)H(4)). However, in the presence of 2.2 molar equiv of Me(3)Al, N-tert-butyl-4-tert-butylbenzamide ((t)BuNHC(p-(t)Bu-C(6)H(4))([double bond]O in refluxing hexane gives [Me(2)Al[eta(2)-(t)BuNC(p-(t)Bu-C(6)H(4))(mu(2)-O)]AlMe(3)], 8. In contrast, the reaction of R'NHCR' '([double bond]O) with 1 molar equiv of R(3)Al at room temperature produces tetracoordinated, dimeric, eight-membered ring aluminum compounds [R(2)Al[mu,eta(2)-R'NC(R' ')O]](2) (9, R = Me, R' = 2,6-(i)Pr, (i)()Pr-C(6)H(3), R' ' = Ph; 10, R = Me, R' = (i)Bu, R' ' = Ph; 11, R = Et, R' = Bn, R' ' = Ph; 12, R = Me, R' = Ph, R' ' = CF(3); 13, R = Me, R' = Bn, R' ' = CF(3)). On the other hand, 4'-chlorobenzanilide ((p-Cl-C(6)H(4))NHCPh([double bond]O)) reacts with R(3)Al to produce trimeric, twelve-membered ring aluminum compounds [R(2)Al[mu, eta(2)-(p-Cl-C(6)H(4))NC(Ph)O]](3) (14, R = Me; 15, R = Et). Furthermore, the reaction of 2'-methoxybenzanilide with 1 molar equiv of Me(3)Al in hexane yields a dinuclear aluminum complex [Me(2)Al(o-OMe-Ph)NC(Ph)(O)AlMe(3)], 16. 相似文献