2,4-Di-tert.-butyl-1,3-dihydroxy-benzol | 18123-52-9

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 2,4-Di-tert.-butyl-1,3-dihydroxy-benzol
• 英文别名: 2,4-Di-tert-butyl-1,3-benzenediol；2,4-ditert-butylbenzene-1,3-diol
• CAS: 18123-52-9
• 化学式: C₁₄H₂₂O₂
• 分子量: 222.327
• InChiKey: NMJMUSGKTCPFOK-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.6
• 重原子数：
  16
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.57
• 拓扑面积：
  40.5
• 氢给体数：
  2
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  2,4-Di-tert.-butyl-1,3-dihydroxy-benzol 在 sodium hydroxide 、 dipotassium hydrogenphosphate 、 potassium nitrososulfonate 作用下， 以 甲醇 为溶剂， 反应 2.0h， 以70%的产率得到4-tert-butyl-5-hydroxycyclohexa-3,5-diene-1,2-dione
  参考文献：
  名称：

  Model Studies of Topaquinone-Dependent Amine Oxidases. 1. Oxidation of Benzylamine by Topaquinone Analogs

  摘要：

  The aerobic oxidation of benzylamine by model compounds of topaquinone, the active site organic cofactor in copper-containing amine oxidases, was studied in order to elucidate the chemical function of the cofactor in substrate oxidation. In this study, topaquinone hydantoin (1(ox)) and a series of 2-hydroxy-5-alkyl-1,4-benzoquinones which differ in the bulk of their alkyl substituent (5, 6, 7, and 8) were employed as model compounds of the cofactor. The p-quinones (9, 10, 11, and 12) and the o-quinones (13 and 14) were prepared in order to compare them to the topaquinone analogs. Benzylamine was oxidized by the topaquinone analogs (1(ox), 5, 6, 7, and 8) to yield N-benzylidenebenzylamine (PhCH=NCH(2)Ph) as a sole product in acetonitrile at room temperature, The quinones bearing a bulky substituent (1(ox), 5, and 6) were found to be more efficient catalysts than those bearing a small primary alkyl group (7 and 8). In the latter case, the dimers (16 and 17) of the substrate Schiff base intermediates (15, R = methyl, ethyl) were isolated. The p-quinones (9, 10, 11, and 12) were catalytically inactive, The o-quinones (13 and 14) had detectable catalytic activity at room temperature, In anaerobic reactions of the o-quinones (13 and 14) with benzylamine, quantitative formation of the product (PhCH=NCH(2)Ph) was observed. For both o-quinones, products and intermediates which support a transamination mechanism were identified by H-1 NMR spectroscopy. The order of reactivity of quinones (5 > 14 > 13) reflects their redox potentials, such that regeneration of quinone may be rate-determining with o-quinones. These results demonstrate a substantial role of the 2-hydroxyl group of the topaquinone in preventing the formation of Michael adducts with substrate amine and in facilitating the reoxidation of aminoresorcinol intermediates.

  DOI：

  10.1021/ja00139a002
• 作为产物：
  描述：

  叔丁醇 、 间苯二酚 在 磷酸 作用下， 以9.5%的产率得到4-叔-丁基苯-1,3-二醇
  参考文献：
  名称：

  Model Studies of Topaquinone-Dependent Amine Oxidases. 1. Oxidation of Benzylamine by Topaquinone Analogs

  摘要：

  The aerobic oxidation of benzylamine by model compounds of topaquinone, the active site organic cofactor in copper-containing amine oxidases, was studied in order to elucidate the chemical function of the cofactor in substrate oxidation. In this study, topaquinone hydantoin (1(ox)) and a series of 2-hydroxy-5-alkyl-1,4-benzoquinones which differ in the bulk of their alkyl substituent (5, 6, 7, and 8) were employed as model compounds of the cofactor. The p-quinones (9, 10, 11, and 12) and the o-quinones (13 and 14) were prepared in order to compare them to the topaquinone analogs. Benzylamine was oxidized by the topaquinone analogs (1(ox), 5, 6, 7, and 8) to yield N-benzylidenebenzylamine (PhCH=NCH(2)Ph) as a sole product in acetonitrile at room temperature, The quinones bearing a bulky substituent (1(ox), 5, and 6) were found to be more efficient catalysts than those bearing a small primary alkyl group (7 and 8). In the latter case, the dimers (16 and 17) of the substrate Schiff base intermediates (15, R = methyl, ethyl) were isolated. The p-quinones (9, 10, 11, and 12) were catalytically inactive, The o-quinones (13 and 14) had detectable catalytic activity at room temperature, In anaerobic reactions of the o-quinones (13 and 14) with benzylamine, quantitative formation of the product (PhCH=NCH(2)Ph) was observed. For both o-quinones, products and intermediates which support a transamination mechanism were identified by H-1 NMR spectroscopy. The order of reactivity of quinones (5 > 14 > 13) reflects their redox potentials, such that regeneration of quinone may be rate-determining with o-quinones. These results demonstrate a substantial role of the 2-hydroxyl group of the topaquinone in preventing the formation of Michael adducts with substrate amine and in facilitating the reoxidation of aminoresorcinol intermediates.

  DOI：

  10.1021/ja00139a002

文献信息

• Organophosphonate co-ester, stabiliser composition containing it and synthetic resin stabilised therewith
  申请人：S.A. Diamond Shamrock Benelux N.V.

  公开号：EP0006842A1

  公开（公告）日：1980-01-23

  New polyhydric phenol coesters are disclosed of polyhydric phenols, having 2 to 3 phenolic hydroxyl groups and 1 to 3 benzenoid rings, with carbonic acid and an organophosphonic acid having linked to phosphorus an alkyl, aryl, aralkyl or alkaryl group optionally substituted with a phenolic hydroxyl group. The new coesters have molecular weights up to a maximum of about 10,000, preferably from 1000 to 9000, and are highly effective stabilizers for a variety of synthetic resins. Stabilizer compositions comprising a polyhydric phenol coester and a known polymer stabilizer, as well as synthetic resins stabilized with such stabilizer compositions, are also disclosed.

  新的多羟基酚共聚物由多羟基酚、碳酸和有机膦酸组成，碳酸和有机膦酸具有 2 至 3 个酚羟基和 1 至 3 个苯环，碳酸和有机膦酸具有与磷相连的烷基、芳基、芳烷基或烷芳烷基，这些烷基、芳基、芳烷基或烷芳烷基可选择被酚羟基取代。新型共聚物的分子量最高可达 10,000 左右，最好在 1000 到 9000 之间，是各种合成树脂的高效稳定剂。 此外，还公开了由多羟基苯酚共聚物和已知聚合物稳定剂组成的稳定剂组合物，以及用这种稳定剂组合物稳定的合成树脂。
• 2,2,6,6-Tetramethyl-4-piperidyl carboxylic acid esters and amides of mono and poly alcohols, phenols and amines and synthetic polymer compositions stabilized thereby
  申请人：ADEKA ARGUS CHEMICAL CO., Ltd.

  公开号：EP0022997A1

  公开（公告）日：1981-01-28

  2,2,6,6-Tetramethyl-4-piperidyl carboxylic acid esters and amides of mono and poly alcohols, phenols and amines are provided, useful as stabilizers for organic polymeric materials, and having the general formula: wherein: R1, R2 and R3 are selected from the group consisting of hydrogen and alkyl having from one to about eighteen carbon atoms; X is oxygen or imino >NH; m is zero, 1 or 2; n is zero, 1 or 2; m + n is 1 or 2; p is zero or 1; q is 1 to 6; is linked to carbon in place of one R2 or R, group; and is selected from the group consisting of: (a) OR5 where R5 is alkyl, aryl or cycloalkyl having one to twenty-four carbon atoms and hydroxy-, carboxy- and oxy-substituted such groups having from one to five OH or O groups; and 2,2,6,6-tetramethyl-4-piperidyl; (b) OReO where Re is alkylene, arylene or cycloalkylene having one to twenty-four carbon atoms and hydroxy-substituted such groups having one to four OH groups; Re alkylene, aryiene or cycloalkylene can include oxyether -0- and thioether -S- linking groups attached to alkylene, arylene or cycloalkylene groups as in polyoxyalkylene and polythioalkylene groups and polyoxyalkylene arylene groups having from one to about five oxy or thio groups and from two to about six alkylene groups having (c) from two to about six carbon atoms; where R6 is alkylene, arylene or cycloalkylene having one to twenty-four carbon atoms and hydroxy-substituted such groups having one to four OH groups; R6 alkylene, arylene or cycloalkylene can include oxyether -O- and thioether -S- linking groups attached to alkylene, arylene or cycloalkylene groups as in polyoxyalkylene and polythioalkylene groups and polyoxyalkylene arylene groups having from one to about five oxy or thio groups and from two to about six alkylene groups having from two to about six carbon atoms; R7 is alkyl, aryl or cycloalkyl having one to twenty-four carbon atoms and hydroxy-substituted such groups having from one to five OH groups; (d) where R5 is alkyl, aryl or cycloalkyl having one to twenty-four carbon atoms and amino-substituted such groups having (e) from one to five amino groups; where R6 is alkylene, arylene or cycloalkylene having one to twenty-four carbon atoms and amino-substituted such groups having one to four amino groups; R7 is alkyl, aryl or cycloalkyl having one to twenty-four carbon atoms and amino-substituted such groups having one to five amino groups; (f)-NHNH2; -NHNH-; -NHNHCOCONHNH2; NHNHCOR7; -NHNHCOR6CONHNH2; -NHNHCOR6CONHNH-; -NHNHCOCONHNH-,; -NHR6NH2-; -NHR6NH-; where Rs is alkylene, arylene or cycloalkylene having one to twenty-four carbon atoms and amino-substituted such groups having one to four amino groups; and such groups including oxyether and thioether linking groups as in (b) above, and R7 is as in (c) above.

  本发明提供了 2,2,6,6-四甲基-4-哌啶基羧酸酯和一元醇和多元醇、酚和胺的酰胺，可用作有机聚合物材料的稳定剂，其通式为 其中 R1、R2 和 R3 选自氢和具有 1 至约 18 个碳原子的烷基组成的组； X 是氧或亚胺 >NH； m 为零、1 或 2 n 为零、1 或 2 m + n 为 1 或 2； p 为 0 或 1 q 为 1 至 6； 与碳相连，代替一个 R2 或 R, 基团；以及 选自以下组成的组 (a) OR5，其中 R5 是具有 1 至 24 个碳原子的烷基、芳基或环烷基，以及具有 1 至 5 个 OH 或 O 基团的羟基、羧基和氧基取代的此类基团；以及 2,2,6,6-四甲基-4-哌啶基； (b) OReO 其中 Re 为具有 1 至 24 个碳原子的亚烷基、芳基或环烷基，以及具有 1 至 4 个 OH 基团的羟基取代的此类基团；Re亚烷基、芳基或环烷基可包括连接到亚烷基、芳基或环烷基上的氧醚 -0- 和硫醚 -S- 连接基团，如聚氧亚烷基、聚硫亚烷基和聚氧亚烷基芳基中的氧醚 -0- 和硫醚 -S- 连接基团，这些基团具有 1 至 5 个氧基或硫代基团和 2 至 6 个亚烷基，这些亚烷基具有 (c) R6是具有一至二十四个碳原子的亚烷基、芳基或环烷基，以及具有一至四个羟基的羟基取代的亚烷基、芳基或环烷基；R6 亚烷基、亚芳基或环烷基可包括连接到亚烷基、亚芳基或环烷基上的氧醚 -O- 和硫醚 -S- 连接基团，如聚氧亚烷基和聚硫亚烷基以及聚氧亚烷基亚芳基中的氧醚 -O- 和硫醚 -S- 连接基团，这些亚烷基、亚芳基或环烷基具有一至约五个氧或硫基和二至约六个亚烷基，这些亚烷基具有二至约六个碳原子；R7 是具有一至二十四个碳原子的烷基、芳基或环烷基，以及具有一至五个羟基的羟基取代的此类基团； (d) 其中 R5 是具有一至二十四个碳原子的烷基、芳基或环烷基和具有 (e) R6 是具有 1 至 24 个碳原子的亚烷基、芳基或环烷基，以及具有 1 至 4 个氨基的氨基取代的此类基团；(f)-NHNH2; -NHNH-; -NHNHCOCONHNH2; NHNHCOR7; -NHNHCOR6CONHNH2; -NHNHCOR6CONHNH-; -NHNHCOCONHNH-,; -NHR6NH2-;-NHR6NH-； 其中 Rs 是具有一至二十四个碳原子的亚烷基、芳烯基或环烷基，以及具有一至四个氨基的氨基取代的此类基团；此类基团包括如上文(b)所述的氧醚和硫醚连接基团，R7 如上文(c)所述。
• 2,6-Di-tertiary butyl phenyl pentaerythritol spiro bis-phosphites enhancing the stability to heat and light of synthetic resins, stabilizer compositions comprising phenolic antioxidants and such phosphites, and synthetic resin compositions containing the same
  申请人：ADEKA ARGUS CHEMICAL CO., Ltd.

  公开号：EP0038876A1

  公开（公告）日：1981-11-04

  2,6-Di-tertiary butyl phenyl pentaerythritol spiro bis-phosphites are provided having the structure: wherein: R is alkyl having from one to six carbon atoms; R is methyl or ethyl; R2 is selected from the group consisting of alkyl having from one up to about eighteen carbon atoms; cycloalkyl having from three up to about twelve carbon atoms; and alkaryl and aryl having from six to about thirty carbon atoms; such groups substituted with from one to about four oxy ether-0- and/or carboxylic ester-COO-groups; the residue of a polyhydric alcohol having from two to about eighteen carbon atoms, and from two to about ten hydroxyl groups; and the residue of a polyphenol having from six to about eighteen carbon atoms and from two to about ten phenolic hydroxyl groups. Stabilizer compositions are provided comprising a phenolic antioxidant and such phosphites as well as synthetic resin compositions having an enhanced resistance to deterioration by heat and/or light due to the presence of such a phosphite and/or stabilizer composition.

  2,6-二叔丁基苯基季戊四醇螺双磷酸盐具有以下结构： 其中 R 是具有 1 至 6 个碳原子的烷基； R 是甲基或乙基 R2 选自具有 1 至约 18 个碳原子的烷基；具有 3 至约 12 个碳原子的环烷基；具有 6 至约 30 个碳原子的烷芳基和芳基；这些基团被 1 至约 4 个氧醚-0-和/或羧酸酯-COO-基团取代；具有 2 至约 18 个碳原子和 2 至约 10 个羟基的多元醇的残余物；以及具有 6 至约 18 个碳原子和 2 至约 10 个酚类羟基的多元酚的残余物。 稳定剂组合物包括酚类抗氧化剂和此类亚磷酸酯以及合成树脂组合物，由于此类亚磷酸酯和/或稳定剂组合物的存在，合成树脂组合物的耐热和/或耐光性得到增强。
• Polyvinyl halide resin compositions containing 1,3 Dicarbonyl compounds
  申请人：PHOENIX CHEMICAL CORPORATION

  公开号：EP0040286A2

  公开（公告）日：1981-11-25

  1,3-Dicarbonyl compounds are provided having the formula: wherein: R1 is selected from the group consisting of hydrogen, hydrocarbon groups having from one to about eighteen carbon atoms and such groups substituted with one or more groups selected from the group consisting of halogen, hydroxy, alkoxy OR1, ester COOR1, alkyl and alkoxycarbonyl alkyl having from one to about eighteen carbon atoms, and R2 is selected from the group consisting of hydrocarbon having from one to about eighteen carbon atoms and such groups substituted with one or more groups selected from the group consisting of halogen, hydroxy, alkoxy OR1, ester COOR1, alkyl and alkoxycarbonyl alkyl having from one to about eighteen carbon atoms; R3 is selected from the group consisting of hydrogen, hydrocarbon groups having from one to about eighteen carbon atoms and such groups substituted with one or more groups selected from the group consisting of halogen, hydroxy, alkoxy OR1, ester COOR1, alkyl and alkoxycarbonyl alkyl having from one to about eighteen carbon atoms; as well as metal and organotin enolate salts thereof. The compounds are effective in enhancing the resistance to deterioration by heat and light of polyvinyl halide resins.

  1,3-二羰基化合物的化学式如下 其中 R1 选自氢、具有 1 至约 18 个碳原子的烃基和被 1 个或多个选自卤素、羟基、烷氧基 OR1、酯 COOR1、烷基和具有 1 至约 18 个碳原子的烷氧羰基烷基的基团取代的此类基团组成的组，和 R2 选自具有 1 至约 18 个碳原子的烃以及被 1 个或多个选自卤素、羟基、烷氧基 OR1、酯 COOR1、烷基和具有 1 至约 18 个碳原子的烷氧羰基烷基的基团取代的烃所组成的组； R3 选自由氢、具有 1 至约 18 个碳原子的烃基以及被 1 个或多个选自由卤素、羟基、烷氧基 OR1、酯 COOR1、烷基和具有 1 至约 18 个碳原子的烷氧羰基烷基组成的基团取代的烃基所组成的组； 以及它们的金属盐和有机锡烯酸盐。 这些化合物可有效提高聚乙烯卤化树脂的耐热和耐光劣化性能。
• Homogeneous storage-stable liquid barium-cadmium-triphosphite stabilizer systems for polyvinyl chloride resins
  申请人：Argus Chemical Corporation

  公开号：EP0047894A2

  公开（公告）日：1982-03-24

  Homogeneous storage-stable liquid stabilizer systems for polyvinyl chloride resins are provided which are substantially soivent-free and have a low viscosity and a minimum flash point of 96°C, containing, as the essential ingredients, a liquid barium carbonate-barium alkyl phenate; a cadmium salt of a branched chain aliphatic carboxylic acid having from about five to about thirteen carbon atoms, and/or of an aromatic carboxylic acid having from about seven to about eleven carbon atoms, and/or of an unsaturated aliphatic carboxylic acid having from about twelve to about twenty-two carbons; and a liquid organic triphosphite in an amount to form a homogeneous storage-stable liquid; the total weight percent of barium and cadmium in the stabilizer system being at least 13%, and the ratio of the weight percent of cadmium to the weight percent of barium being within the range from about 0.5:1 to about 1.5:1; optionally together with any one or more of a soluble zinc salt of a carboxylic acid, a soluble phenolic antioxidant, a liquid organic acid phosphite, and a soluble carboxylic acid.

  本发明提供了用于聚氯乙烯树脂的贮存稳定的均相液体稳定剂体系，该体系基本上不含溶剂，具有低粘度，最低闪点为96°C，其基本成分包括液体碳酸钡-烷基酚钡；具有约 5 至约 13 个碳原子的支链脂肪族羧酸的镉盐，和/或具有约 7 至约 11 个碳原子的芳香族羧酸的镉盐，和/或具有约 12 至约 22 个碳原子的不饱和脂肪族羧酸的镉盐；和液态有机三亚磷酸，其用量可形成均匀的储存稳定液体；稳定剂体系中钡和镉的总重量百分比至少为 13%，镉的重量百分比与钡的重量百分比之比范围在约 0.5:1至约1.5:1的范围内；可选择与羧酸的可溶性锌盐、可溶性酚类抗氧化剂、液态有机亚磷酸酯和可溶性羧酸中的任意一种或多种一起使用。