2,6-Dimethoxyphenyl Derivatives of a Variety of Elements

2,6-二甲氧基苯基多种元素的衍生物

• 批准号: 08455429
• 负责人: WADA Masanori
• 金额: $ 3.01万
• 依托单位: TOTTORI UNIVERSITY
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (B)
• 财政年份: 1996
• 资助国家: 日本
• 起止时间: 1996 至 1998
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-08455429/
• 关键词: 2,4,6-Trimethoxyphenyl; 2,6-Dimethoxyphenyl; Carbenium; Ferrocenyl; Organosulfur; Organoselenium; Organotellurium; 9-Phenylxanthenylium; 2,4,6-トリメトキシフェニル基; 2,6-ジメトキシフェニル基; ジアリールカルベニウム; フェロセニルカルベニウム; 2,4,6-トリメトキシフェニル; トリアリールカルベニウム塩; ジアリールカルベニ

Abbr.phi^a= 2,4,6-(MeO)3C6H2- ; phi^a= 2,6-(MeO)2C6H3-.1. phi^aCOH reacted with a slight excess of acids to give carbenium salts [phi^a_3]X.Neutralization of 1 M acidic solution of [phi^a_3] resulted in the substitution of one of the para-methoxy groups. [phi^a_2]CHOH also reacted with perchioric acid to give [phi^a_2]CH_4, which was reduced in alcohols to give phi^a_2CH_<2->.2. phi^a_2CHOH reacted with acetone in the presence of catalytic amount of an acid to give phi^a_2CHCH_2COme. Me. Analogous reactions were observed with diethyl ketone, methyl phenyl ketone, propanal, and butanal. phi^a_2CHOH was reduced in alcohols or THF to give phi^a_2CH_2.3. Fc-CHphi^aOH [Fc= ferrocenyl group] reacted with a slight excess of an acid to give [Fc-CHphi^a]X(pKr+=3.0). The salt was reduced in 2-propanol to give Fc-CH_2phi^a and reacted with phi^b-CHphi^a_2,4. On treatment of p-HOcphi^b_2C_6H_4CAphi^bOH(Ar=phi^b, 4-MeOC_6, 4-MeOC_6H_4) with an acid, the Ar-group migrated onto the phenylene group.5. The reactivities of l, 8-dlrnethoxy-9-phenylxanthen-9-ol were compared with those of without difficulty.6. Novel method of preparation of triarymetals MAr_3(M=As, Sb, Bi) was developed. It is composed of the preparation of M(Sphi^b)_3 from metal oxides and phi^bSH and the reaction with LiAr. Both phiSH and M(Sphi^b)_3 are crystalline, and they can be handled without difficulty.7. Nucleophilic reaction rates of phi^b_2E increased in the order E= S <Se <Te, which were compared with those of phi^b_3 (M= P > As> Sb). The rates of phi^b_2EO increased in the order E= S <Se <Te).

缩写phi^a= 2，4，6-（MeO）3C 6 H2- ; phi^a= 2，6-（MeO）2C 6 H3-。φ ^aCOH与略微过量的酸反应，得到碳鎓盐[φ ^a_3]X。[φ ^a_3]的1 M酸性溶液的中和导致对甲氧基之一的取代。[phi[phi_a_2]CHOH也与高氯酸反应生成[phi_a_2]CH_4，其在醇中还原生成<2->phi_a_2CH_2。phi_a_2CHOH在催化量的酸存在下与丙酮反应得到phi_a_2CHCH_2COme。用二乙基酮、甲基苯基酮、丙醛和丁醛观察到类似的反应。在醇或THF中还原phi^a_2CHOH，得到phi^a_2CH_2.3。Fc-CHphi 2aOH [Fc=二茂铁基]与略微过量的酸反应，得到[Fc-CHphi 2aOH]X（pKr+=3.0）。该盐在2-丙醇中还原得到Fc-CH_2 phi ^a，并与phi^b-CH_2 phi ^a_2，4反应。p-HOcphi^B_2C_6 H_4CAphi^bOH（Ar=phi^B，4-MeOC_6，4-MeOC_6 H_4）经酸处理后，Ar-基团迁移到亚苯基上.比较了1，8-二甲氧基-9-苯基咕吨-9-醇的反应性.提出了一种制备三价金属MAr_3（M=As，Sb，Bi）的新方法。它包括由金属氧化物和phi^bSH制备M（Sphi^B）_3以及与LiAr反应。phiSH和M（Sphi^B）_3都是晶体，它们可以毫无困难地处理.与phi^b_3（M= P &gt; As&gt; Sb）相比，phi^b_2E的亲核反应速率按E= S &lt;Se &lt;Te的顺序增大。phi_b_2EO的速率按E= S &lt;Se &lt;Te的顺序增加。

项目成果

Masanori Wada: "Reactions of 1, 8-Dimethoxy-9-phenylxanthen-9-ol in the Presence of an Acid, and its Basicity" Bull.Chem.Soc.Jpn.72(印刷中). (1999)

Masanori Wada：“1, 8-二甲氧基-9-苯基xanthen-9-醇在酸存在下的反应及其碱度”Bull.Chem.Soc.Jpn.72（出版中）。

WADA,Masanori: "Formation of 3-Methylene-1,4-cyclohexadienes from alpha, alpha, alpha', alpha'-Tetraaryl-1,4-benzenedimethanols by the Intramolecular Migration of an Aryl Group" Bull.Chem.Soc.Jpn.Vo.70 (6). 1413-1420 (1997)

WADA，Masanori：“通过芳基的分子内迁移从 α, α, α, α-四芳基-1,4-苯二甲醇形成 3-亚甲基-1,4-环己二烯” Bull.Chem.Soc.Jpn

M.Wada, S.Natsume, S.Suzuki, A.Uo, M.Nakamura, S.Hayase, and T.Erabi: "Two-step synthesls of trlarylmetals (As,Sb,Bi) starting from the metal oxides and 2,6-dimethoxybenzenethiol" J.Organometal.chem.548. 223-227 (1997)

M.Wada、S.Natsume、S.Suzuki、A.Uo、M.Nakamura、S.Hayase 和 T.Erabi：“从金属氧化物和 2 开始两步合成三芳基金属 (As,Sb,Bi)

WADA,Masanori: "Unusual Stabilities and Reactivities of Tris-and Bis (2,4,6-trimethoxyphenyl) carbenium Salts" Bull.Chem.Soc.Jpn.Vol.70 (11). 2737-2741 (1997)

WADA，Masanori：“三-和双（2,4,6-三甲氧基苯基）碳鎓盐的异常稳定性和反应性”Bull.Chem.Soc.Jpn.Vol.70 (11)。

Masanori Wada: "Formation of 3-Methylene-1, 4-cyclohexadienes from α, α, α′, α′-Tetraaryl-1,4-benzenedimethanols by the Intramolecular Migration of an Aryl Group" Bull.Chem.Soc.Jpn.70(6). 1413-1420 (1997)

Masanori Wada：“通过芳基的分子内迁移从 α, α, α, α-四芳基-1,4-苯二甲醇形成 3-亚甲基-1, 4-环己二烯” Bull.Chem.Soc.Jpn. 70（6）。1413-1420（1997）。