脂环族和芳香族二元醇

对1,4-环己烷二甲醇、环己二醇、三环十二碳二甲醇、十二碳环烷二醇、螺环二醇、对苯二酚双羟乙基醚、间苯二酚双羟乙基醚等可用于高分子合成的特种二醇进行了简要介绍,并介绍了它们的性能特点和用途。     

Reaction of CH-acidic compounds with thiacumulenes and alkylation with dihaloalkanes

Dithiocarboxylation of CH-acidic compounds 1 and stepwise alkylation of primarily formed dithiolates 2 yielded ketene dithioacetals 5a,b or methylenebis(dithiocarbonates) 12a–c. Reaction of 5a,b with nucleophiles afforded thiophene 7 and dithioacetals 8, 9a,b, 11, respectively. 1,3-Thiazetidines 14a,c,e and thiazolidines 14b,d,f were prepared by thiocarbamoylation of 1b,c,e and subsequent alkylation with dihaloalkanes.     

聚酯二元醇合成聚氨酯丙烯酸酯复合乳液的研究

以异佛尔酮二异氰酸酯(IPDI)、自制聚酯二元醇、二羟甲基丙酸(DMPA)和甲基丙烯酸甲酯(MMA)、苯乙烯(St)、丙烯酸丁酯(BA)为主要原料,合成了聚酯型聚氨酯丙烯酸酯(PUA)复合乳液,研究了不同相对分子质量的聚酯二元醇、聚氨酯制备时不同NCO/OH比值、添加三羟甲基丙烷(TMP)含量、及合成PUA时不同PU/PA的比值对最终制备的聚氨酯丙烯酸酯复合乳液及涂膜性能的影响。结果表明:1500～2000相对分子质量的聚酯二元醇:在TMP添加量为2%、NCO/OH为1.6～1.8,PU/PA以4︰6合成出的PUA,有着较好的制备稳定性和贮存稳定性,其涂膜硬度、耐水性和耐醇性较好。     

The synthesis of polymeric sulfides by reaction of dihaloalkanes with sodium sulfide

Several poly(alkylene sulfide)s have been synthesized in excellent yields from reactions of α,ω -dibromo- and/or α,ω-dichloroalkanes with sodium sulfide nonahydrate under reflux conditions. The procedure is general, simple and convenient for the production of various poly(alkylene sulfide)s and the way reaction parameters influence the properties of the polymers formed has been examined.

     

Synthesis and Characterization of Novel Diol,Diacid and Di-isocyanate from Oleic Acid

Novel linear diol 2, diacid 3, and diisocyanate 4 with functional groups located at each end of the chain have been produced from oleic acid via a diester precursor. All the compounds were fully characterized by IR, ¹H NMR, ¹³C NMR and Mass Spectrometry. These unbranched terminally-functionalized compounds are important monomers for the manufacture of biodegradable thermoplastic polyurethanes and polyesters. The general synthetic scheme should also prove useful for the syntheses of diols, diacids and diisocyanates from any unsaturated fatty acid.     

长链二元酸和二元醇合成聚酯的研究

以长链二元酸和二无醇为反应单体,采用熔融缩聚的方法合成了聚酯,对合成产物进行了红外吸收光谱（FTIR）、核磁共振氢谱（＇H NMR）和凝胶色谱（GPC）等表征。研究了醇酸比、反应单体、催化剂种类、催化剂用量、抽真空时间等因素对合成产物结构的影响。     

From Arene Oxides to Diol Epoxides and DNA

Although the polycyclic aromatic hydrocarbons (PAH) are structurally less complex compared to many other compounds with high biological activity, their metabolism, the chemical reactivity of their metabolites, and the mutagenicity and tumorigenicity of these metabolites have stimulated intensive research into their mechanisms of action. The present report focuses on our contributions to the identification of bay-region and fjord-region diol epoxides as ultimate carcinogens of the PAH and describes some of the remarkable stereochemical control involved in their synthesis, metabolic formation, and expression of tumorigenic activity.     

Novel Long‐Chain Diol Phospholipids from Some Bacteria Belonging to the Class Thermomicrobia

Polar lipids of bacteria from the class Thermomicrobia are known to contain long‐chain 1,2‐diols instead of glycerol, although the nature of polar head groups has not been investigated. We have studied phospholipid classes of two species from the class Thermomicrobia—Sphaerobacter thermophilus and Thermomicrobia sp. WKT50.2. TLC and ³¹P‐NMR analysis of polar lipids revealed that both S. thermophilus and Thermomicrobia sp. WKT50.2 contain the same set of four major phospholipid classes. Structures of the novel phospholipids in S.thermophilus were established as 2‐acylalkyldiol‐1‐O‐phosphoinositol, 2‐acylalkyldiol‐1‐O‐phosphoinositol mannoside, 2‐acylalkyldiol‐1‐O‐phospho‐acylmannoside, and 2‐acylalkyldiol‐1‐O‐phosphoinositol acylmannoside. To our knowledge, this is the first report of a phospholipid with a mannose directly bound to the phosphate. We also analyzed fatty acids and long‐chain 1,2‐diols of S. thermophilus and Thermomicrobia sp. WKT50.2 and compared our data with available information for T. roseum. All species share a similar set of fatty acids, with 12‐Me 18:0 being the major fatty acid. The major diol in S. thermophilus was identified as 13‐Me 19:0 (66.2 %). The 21:0 diol was the major component both in Thermomicrobia sp. WKT50.2 (50.6 %) and in T. roseum (56.6 %).     

二元醇改性酸酐增韧剂的合成与性能测试

环氧固化体系中,需要提高韧性,通过二元醇改性过的甲酸酐是比较优秀的增韧剂,加入2-4%就能使得本体拉伸强度、弯曲强度和断裂伸长率得到提高,同时玻璃化转变温度降低幅度较小。     

NMR Solution Structures of Adducts Derived from the Binding of Polycyclic Aromatic Diol Epoxides to DNA

Site-specifically modified oligonucleotides were derived from the reactions of stereoisomeric polycyclic aromatic diol epoxide metabolite model compounds with oligonucleotides of defined base composition and sequence. The NMR solution structures of ten different adducts studied so far are briefly described, and it is shown that stereochemical factors and the nature of the oligonucleotide context of the complementary strands, exert a powerful influence on the conformational features of these adducts.     

聚氨酯用二聚酸聚酯二醇的合成

研究了以辛酸亚锡为催化剂、二聚酸（DA）与乙二醇（EG）为原料、制备聚氨酯用二聚酸聚酯二醇的方法,讨论了催化剂的类型和用量、反应温度、原料醇酸比、反应时间等对酯化率的影响,并用红外光谱对合成产物进行了表征。结果表明,DA与EG摩尔配比为1：2．4,催化剂辛酸亚锡用量为原料总质量的0．3％,反应温度在1h内缓慢升温到190℃,然后保温反应4h,并在130℃、2．66kPa下减压3h,酯化率可达99．7％,产品羟值为95mgKOH／g,酸值0．26mgKOH／g。     

Diol Lipids New Types of Naturally Occuring Lipid Substances

Lipids of plants, animals and microorganisms frequently contain minor amounts of lipophylic derivatives of ethyleneglycol and related lower dihydric alcohols, which mostly have been overlooked in the part. Methods for the quantitative determination of diols in lipid hydrolyzates have been developed. In some particular cases, e. g. lipids of marine invertebrates, regenerating rat liver and young corn seeds comparatively high diol/glycerol ratios were found. Various methods for the structural investigation of diol lipids, including mass-spectrometry and combined GLC-mass-spectrometry are described. The chemical structure of a number of diol lipids including simple neutral lipids, diol galactolipids and diol cholinephosphatides has been clarified, the existence of other types is probable. The biosynthetic pathways of the diol lipids seem to be similar to those of the glycerolipids.     

聚氨酯用丁二酸聚酯二醇的合成

研究了以丁二酸、乙二醇为主要原料制备聚氨酯用丁二酸聚酯二醇的方法,考察了原料酸醇比、反应温度、催化剂种类及用量、反应时间等对反应的影响。结果表明,当丁二酸与乙二醇摩尔比为1∶1.8、催化剂为辛酸亚锡、用量为原料总质量的0.3%、预酯化反应温度为180℃、减压缩聚温度为160℃、时间为5 h、真空度1.99 kPa时,酯化率达到99%,产品羟值为105 mgKOH/g,酸值为0.91 mgKOH/g。     

聚己内酯—共聚醚制备聚氨酯弹性体的研究

以聚己内酯、四氢呋喃－环氧丙烷共聚醚、甲基二异氰酸酯、ＭＯＣＡ等为原料,制备了浇注型聚氨酯弹性体了聚己内酯与共聚醚的比例、ＮＣＯ质量分数、增塑剂与ＭＯＣＡ用量比例对弹性体力学性能的影响。以最佳工艺条件制得的弹性体,其性能为：邵尔Ａ型硬度为５７￣５８,３００％模量３．８￣３．９ＭＰａ,拉伸强度１８．５￣１９．５ＭＰａ,扯断工率４５０￣４６０％,撕裂强度２８￣３０ｋＮ／ｍ。     

聚酯二元醇合成聚氯酯丙烯酸酯复合乳液的研究

以异佛尔酮二异氰酸酯（IPDI）、自制聚酯二元醇、二羟甲基丙酸（DMPA）和甲基丙烯酸甲酯（MMA）、苯乙烯（St）、丙烯酸丁酯（BA）为主要原料,合成了聚酯型聚氨酯丙烯酸酯（PUA）复合乳液,研究了不同相对分子质量的聚酯二元醇、聚氨酯制备时不同NCO／OH比值、添加三羟甲基丙烷（TMP）含量、及合成PUA时不同PU／PA的比值对最终制备的聚氨酯丙烯酸酯复合乳液及涂膜性能的影响。结果表明：1500～2000相对分子质量的聚酯二元醇：在TMP添加量为2％、NCO／OH为1．6～1．8,PU／PA以4：6合成出的PUA,有着较好的制备稳定性和贮存稳定性,其涂膜硬度、耐水性和耐醇性较好。     

Tumorigenicity of Fjord Region Diol Epoxides of Polycyclic Aromatic Hydrocarbons

(±)-anti-Benzo[c]phenanthrene-3,4-diol-1,2-epoxide (BcPDE), (±)-anti-benzo[g]-chrysene-11,12-diol-13,14-epoxide (BgCDE), and (±)-anti-dibenzo[a,l]pyrene-11,12-diol-13,14-epoxide (DB[a,l]PDE) were synthesized for use in biological assays. To compare mammary carcinogenicity, BcPDE and (±)-anti-benzo[a]pyrene-7,8-diol-9,10-epoxide (BPDE) were tested by direct application to the mammary glands of female CD rats at a total dose of 12.2 μmol per animal. 6-Nitrochrysene (6-NC) at the same dose was used as a positive control. BcPDE was found to be a potent mammary tumorigen and carcinogen, inducing significantly more fibroadenomas and adenocarcinomas than the other two compounds. In a second bioassay, BcPDE, BgCDE, and DB[a,l]PDE at a total dose of 1.2 μmol were compared. All three diol epoxides were potent mammary carcinogens and based on the collective results to date, the relative carcinogenic activities of the diol epoxides can be approximated as DB[a,l]PDE>BcPDE>BgCDE>BPDE.

To determine tumorigenic potencies in newborn mice, BPDE was compared with BgCDE, DB[a,l]PDE, and BcPDE at a total dose of 25 nmol per mouse, administered on days 1, 7, and 15 of life. BgCDE and BcPDE had similar potency in inducing lung tumors. BgCDE induced more liver tumors in male mice than BcPDE. Both compounds were more tumorigenic than BPDE. DB[a,l]PDE was highly toxic at 25 nmol and all animals died within one week after the first dose. DB[a,l]PDE was also tested at total intended doses of 5 nmol and 1 nmol. Due to high toxicity, only the first dose of the intended 5 nmol was given. This dose as well as the 1 nmol total dose caused significant incidence and multiplicity of lung tumors.

These results support the hypothesis that sterically hindered fjord region diol epoxides are potent mammary carcinogens in CD rats and strong lung tumorigens in newborn mice.     

酯交换法合成聚碳酸酯二元醇研究的进展

介绍了聚碳酸酯二元醇的用途、优点及合成方法。综述了使用均相催化剂(碱金属化合物催化剂、碱土金属化合物催化剂、有机金属化合物催化剂、有机胺类催化剂)和多相作化剂(水滑石类催化剂、负载型催化剂、酶催化剂)合成聚碳酸酯二元醇的研究进展。总结了合成聚碳酸酯二元醇过程中遇到的问题并提出了解决方法。     

Potential synthetic lubricants: Diol ester of C18-saturated cyclic acids

Monoalkyl esters of linseed-oil-derived C₁₈-saturated cyclic acids (HCal), described in earlier work, showed promise as lubricant base stocks for turbine aircraft as set forth in the military specification MIL-L-7808E. These esters, however, did not exhibit the increased oxidative stability and higher viscosity required by the more recent specification MIL-L-23699. Six diol esters of HCal have now been prepared. Both hindered and unhindered dihydric alcohols were used, including ethylene glycol, 1,4-cyclohexanedimethanol, 1,4-benzenedimethanol, 2,3-dimethyl-1,3-propanediol and 2,2,4,4-tetramethyl-1,3-cyclobutanediol (I). The viscosities of these esters at 210F ranged from 10.1 to 19.6 centistokes and the pour points, from −35 to −62F. Oxidative stabilities at 400F were determined with 0.5% each of phenyl-a-napthylamine (PANA) andp,p’-dioctyldiphenylamine as inhibitors. The esters of the unhindered diols had poor stability, whereas esters of the hindered diols, in particular I, exhibited excellent resistance to the formation of acidic decomposition products and sludge. Although the HCal ester of I by itself is too viscous to meet specification MIL-L-23699, its ASTM slope (0.650) is excellent. Blends of this material with less viscous hindered esters, commercially available, may find application as lubricants for high-performance turbine engines used in various aircraft. Presented at the AOCS Meeting in Los Angeles, 1966. No. Utiliz. Res. Dev. Div., ARS, USDA.     

二元醇双琥珀酸双酯磺酸钠(GMI-02)的合成

采用1,4-丁二醇、马来酸酐、月桂醇为主要原料和环境友好的工艺路线,合成了一种易降解的双子(Gemini)表面活性剂--二元醇双琥珀酸双酯磺酸钠(GMI-02)。对各步合成条件采用正交实验进行优化,得出各步反应的优化工艺条件:酯化反应I,配比为n(1,4-丁二醇)∶n(马来酸酐)=1∶2.15,反应时间2h,催化剂w(乙酸钠)=1.0%,反应温度95℃,以丙酮作溶剂,回流操作;酯化反应Ⅱ,甲苯为溶剂,反应时间6h,反应温度145℃,催化剂w(对甲苯磺酸)=1.0%,n(1,4-丁二醇双马来酸单酯)∶n(月桂醇)=1∶2.20。磺化反应,石蜡加热,石蜡温度(加热温度)控制在115℃,时间为6h,原料配比为n(1,4-丁二醇双马来酸双酯)∶n(亚硫酸氢钠)=1∶2.50。对每步合成产物均用IR进行了表征。