N-烷基-4-哌啶酮类化合物的合成

对N 烷基 4 哌啶酮类化合物的合成进行了研究,重点对其中的正丁基、正己基、正辛基、苄基取代物进行了合成。以胺类化合物为原料,与丙烯酸甲酯经过两次Michael加成得到N,N 二丙酸甲酯类化合物,该化合物在甲醇钠存在下进行环合,在酸性条件下脱羧,高收率得到4 哌啶酮类化合物,从而证明了这是一条合成N 取代 4 哌啶酮类化合物的普遍方法。     

吡咯并[2,3-c]氮杂卓-4,8-二酮衍生物的合成

将N-(2-吡咯甲酰基)-β-丙氨酸甲酯(Ⅲ)与卤代烃经烷基化反应得到的产物水解,得到N-(1-烷基-2-吡咯甲酰基)-β-丙氨酸(Ⅱa～Ⅱc),收率84.7%～91.2%;以化合物Ⅱ为原料,在多聚磷酸-P2O5作用下,经分子内环化反应合成了标题化合物1-烷基-6,7-二氢-1H,5H-吡咯并[2,3-c]氮杂-4,8-二酮(Ⅰa～Ⅰc),收率69.1%～77.2%。3步反应总收率为61.8%～69.1%。测定了3个标题化合物对α-葡萄糖苷酶的抑制作用。     

1-乙酰基-3-烷基奠类衍生物的合成

以环庚并呋喃-2-酮-3-羧酸酯为初始原料,在分子筛的催化作用下,与脂肪醛、吗啡啉进行[8＋2]环化加成,制得3-烷基奠-1-羧酸甲酯,采用三氯乙酸进行脱羧反应,得到1-烷基莫,最后经Vilsmeier-Haack反应,在N,N-二甲基乙酰胺和三氯氧磷作用下得到高收率的标题化合物。     

1-乙酰基-3-烷基薁类衍生物的合成

以环庚并呋喃-2-酮-3-羧酸酯为初始原料,在分子筛的催化作用下,与脂肪醛、吗啡啉进行[8+2]环化加成,制得3-烷基奠-1-羧酸甲酯,采用三氯乙酸进行脱羧反应,得到1-烷基奠,最后经Vilameier-Haack反应,在N,N-二甲基乙酰胺和三氯氧磷作用下得到高收率的标题化合物.     

2-叔丁氧羰基-9-乙氧羰基-2,7-二氮杂-螺[4.4]壬烷的合成

报道了2-叔丁氧羰基-9-乙氧羰基-2,7-二氮杂-螺[4.4]壬烷的合成方法,即以甘氨酸乙酯盐酸盐■为起始原料,与丙烯酸乙酯■经迈克尔加成、 Boc保护和分子内迪克曼缩合生成3-乙氧羰基-4-吡咯酮(■)和2-乙氧羰基-3-吡咯酮(■)后,经Krapcho脱羧反应生成N-Boc-3-吡咯酮(■),随后与磷酰乙酸三乙酯经Witting-Horner-Emmons反应生成α,β-不饱和羧酸乙酯(■),再经[1,3]-偶极环加成反应生成螺环双吡咯烷(■),最后经氢解脱去苄基等7步反应得到标题化合物2-叔丁氧羰基-9-乙氧羰基-2,7-二氮杂-螺[4.4]壬烷(TM),总收率为11%,中间体和目标产物结构经~1H NMR和MS确证。     

正己基和正辛基异氰酸酯的合成

在甲苯溶液中,用固体光气为原料,分别与正己胺和正辛胺在0～5℃反应,中间产物在70℃以上分解合成异氰酸酯,常压蒸馏除去甲苯,减压蒸馏得到正己基和正辛基异氰酸酯。加入少量氢化钙能够降低异氰酸酯的三聚成环副反应,正己基和正辛基异氰酸酯收率分别达72.5%和77.9%,折光指数分别为1.4203和1.4298,纯度达99.0%以上。     

3-[双(苯甲硫基)亚甲基]-2,4-戊二酮的合成和晶体结构

以2,4-戊二酮为底物,碳酸钾为拔氢试剂,在N,N-二甲基甲酰胺中与二硫化碳进行亲核加成,然后与苄基溴发生亲核取代合成标题化合物。并经过IR、1HNMR和X-单晶衍射对化合物进行了表征。     

N,N''''-二正辛基-3,3''''-二硫代二丙酰胺的合成

研究了异噻唑啉酮的关键中间体N,N'-二正辛基-3,3'-二硫代二丙酰胺的合成。以丙烯酸甲酯为原料,经亲核加成、脱硫精制及酰胺化反应制得目的产物,总收率可达80%。同时详细讨论了反应物配比、反应温度及时间等因素对收率的影响。     

N，N′-二正辛基-3，3′-二硫代二丙酰胺的合成

研究了异噻唑啉酮的关键中间体N，N′-ZiE辛基-3，3′-二硫代二丙酰胺的合成。以丙烯酸甲酯为原料，经亲核加成、脱硫精制及酰胺化反应制得目的产物，总收率可达80％。同时详细讨论了反应物配比、反应温度及时间等因素对收率的影响。     

5-(4-烷基苯基)-2-(4-氰基苯基)-嘧啶的合成

对 5 (4 烷基苯基 ) 2 (4 氰基苯基 ) 嘧啶的合成进行了研究 ,以 5 (4 正己基苯基 ) 2 (4 氰基苯基 ) 嘧啶 (Ⅳ )的合成为例 ,论述了以 4 己基苯乙酸为原料 ,先依次制得 4 己基苯乙酰氯 ,1 二甲氨基 3 二甲亚胺基 2 (4 正己基苯基 ) 丙烯 高氯酸盐 (Ⅰ ) ,得率 84%。进而在甲醇钠存在下与 4 溴苯基脒盐酸盐 (Ⅱ )相对接 ,合成 5 (4 正己基苯基 ) 2 (4 溴苯基 ) 嘧啶 (Ⅲ ) ,得率 87%。最后Ⅲ和CuCN反应合成了液晶化合物Ⅳ ,得率 78%。其结构由1HNMR和IR光谱所证实 ,同时还测定了其DSC。另外在合成Ⅱ时 ,必须在无水条件下进行 ,而且在通入氯化氢气体时 ,反应温度保持 - 5～ 0℃ ,其反应得率 97%。     

2-甲基薁类衍生物的合成

以环庚并呋喃-2-酮-3-羧酸酯为初始原料,在分子筛的催化作用下,与丙酮、二乙胺进行[8 2]环化加成,制得2-甲基薁-1-羧酸甲酯,采用100%磷酸进行脱羧反应,以92%收率得到2-甲基薁。所合成化合物的结构经核磁共振、红外光谱及元素分析数据证实。     

Fluorescence formation from hydroperoxide of phosphatidylcholine with amino compound

The hydroperoxides of methyl linoleate, 1-palmitoyl-2-linoleoyl-phosphatidylcholine and trilinolein each produced similar fluorescent substances through reaction with amino compounds after decomposition by heme methyl ester. Fluorescent substances formed from methyl linoleate with 1-aminopentane revealed characeristic fluorescence peaks on HPLC, while those obtained from 1-palmitoyl-2-linoleoyl-phosphatidylcholine and trillinolein were not eluted under the same conditions. However, when both of these fluorescent substances were transesterified to methyl ester, the same fluorescence peaks were observed. This result suggests that fluorescent substances formed from oxidized membrane lipids with amino compounds remain attached to phospholipids without being released from their glycerol backbone.     

替诺昔康的中间体合成研究

以3-氨基-2-噻吩甲酸甲酯为原料,经氯磺化、甲胺化、N-烷基化、环合等反应合成了替诺昔康的中间体4-羟基-3-甲基-2H-噻吩并[2,3-e]-1,2-噻嗪-2-羧酸甲酯-1,1-二氧化物(MHTTCD)。氯磺化时在大大减少溶剂(醋酸)用量的条件下,收率为78%,甲胺化收率为81.6%。环合反应在甲醇钠的甲醇溶液中进行,合适的甲醇钠浓度为1mol/L。回流反应1h,该步收率达55.5%。合成路线反应总收率为11.11%。通过GC-MS确认了各中间体的结构。由于N-烷基化时以氯乙酸乙酯代替肌氨酸乙酯盐酸盐以及收率的提高,降低了合成成本。     

Evaluation of fat-derived aroma compounds in blue cheese by dynamic headspace GC/Olfactometry-MS

The aroma compounds in Blue cheese were studied with a dynamic headspace-GC/olfactometry (GC/O-DH) technique and evaluated by both aroma extract dilution analysis (AEDA) and the Osme technique to identify and assign importance to aroma compounds. AEDA aroma dilution values were obtained by sequential reduction of sample size, and Osme values were obtained based on aroma intensity and duration. The most important compounds contributing to Blue cheese aroma were diacetyl, 2-methylpropanal, 3-methylbutanal, ethyl butanoate, ethyl hexanoate, methional, dimethyl trisulfide, 2-heptanone, and 2-nonanone. Compounds central to the characteristic Blue cheese aroma and typically derived from milkfat included 2-heptanone, 2-nonanone, butanoic acid, hexanoic acid, and ethyl esters. Since the methyl ketones contributed the characteristic Blue cheese aroma, a flavor concentrate enriched in methyl ketones to impart characteristic Blue cheese aroma was synthesized using Penicillium roqueforti spores in a model system. A fivefold enhancement in methyl ketone production was obtained by providing aerobic conditions. The addition of sucrose and serine, compounds known to affect mold spore metabolism, did not enhance methyl ketone production but caused generation of an uncharacteristic fruity, floral aroma.     

Hydrogen sulfide adducts of methyl oleate and linoleate

Sulfur compounds derived from photochemical addition of hydrogen sulfide to methyl oleate and linoleate were separated by preparative gas chromatography. The major compounds were investigated by NMR, mass and IR spectroscopy and by elemental analysis. The primary product of the methyl oleate reaction was methyl 9(10)-mercaptostearate. Gas chromatograms of the product from methyl linoleate showed four principal peaks. From mass spectra and NMR data, we identified methyl 9-(2-pentyl-1-thiolan-5-yl)nonanoate, methyl 8-(2-hexyl-1-thiolan-5-yl)octanoate and methyl 9-(3-hexyl-1,2-dithiolan-5-yl)nonanoate. Evidence for the formation of methyl mercapto-octadecenoates and methyl dimercaptostearates was also obtained. ARS, USDA.     

脱氢松香酸甲酯呋咱衍生物的合成与表征

以歧化松香为原料,将其纯化得到脱氢松香酸,用硫酸二甲酯酯化后,通过12位溴代、7位氧化、13位硝化得到7-羰基-12-溴-13-硝基脱氢松香酸甲酯(Ⅴ),Ⅴ经过与叠氮化钠反应后,在甲苯中回流关环得到7-羰基-12,13-氧化呋咱脱氢松香酸甲酯(Ⅶ),Ⅶ再用三苯基膦脱氧得到7-羰基-12,13-呋咱脱氢松香酸甲酯Ⅷ,这两种产物的产率分别为83%和76%;产物经IR、1HNMR1、3CNMR和MS进行了表征。     

用Wittig和Wittig-Horner反应合成藏红花酸二甲酯

以短碳链化合物1,4-二溴-2-丁烯、丙酮醛缩二甲醇、2-溴丙酸甲酯和氯乙醛为起始原料,首先分别合成2,7-二甲基-2,4,6-辛三烯-1,8-二醛和γ-氯代惕各酸甲酯,然后将两者结合而成藏红花酸二甲酯。合成过程中碳碳双键的形成为关键步骤。通过比较Wittig和Wittig-Horner反应在双键形成中的作用,得出结论:合成2,7-二甲基-2,4,6-辛三烯-1,8-二醛时,宜用Wittig-Horner反应,产率为58.7%;合成γ-氯代惕各酸甲酯和藏红花酸二甲酯时,宜用Wittig反应,产率分别为74.3%和78.6%。     

新型没食子酸二聚体液晶的合成与性能

以没食子酸甲酯为原料,通过醚化反应合成含十二烷基的没食子酸衍生物2。该衍生物进一步与水合肼肼解得到含十二烷基的没食子酸酰肼3。化合物3再与对苯二甲醛反应,合成了新型十二烷基没食子酸席夫碱二聚体4,分离简便,产率高。新化合物的结构经红外、核磁和质谱表征。差热分析和偏光显微镜观察表明,其具有很好的液晶性能。     

NMR chemical shift reagents in structural determination of lipid derivatives: III. Methyl ricinoleate and methyl 12-hydroxystearate

Chemical shift reagents (CSR) can substantially increase the amount of structural information obtainable from NMR studies of saturated and unsaturated lipid derivatives. It is theoretically possible to obtain even more information from CSR studies of unsaturated lipid derivatives by introducing additional CSR-active functional groups into those molecules through derivatization of their double bonds. However additional CSR coordination sites complicate spectral interpretation, because they increase the number of signals that overlap. Therefore two model compounds were investigated to test the feasibility of attempting other CSR analyses of polyfunctional molecules of unknown structure. This paper describes successful CSR studies of methyl ricinoleate and methyl 12-hydroxystearate. A series of complementary interpretive techniques was used to assign proton signals in spectra obtained during incremental Eu(fod)₃ addition studies with these compounds. Individual proton signals can be observed and assigned for all the protons in methyl ricinoleate, except those on carbons 5, 6 and 7. Information obtained for methyl 12-hydroxystearate is less specific. Signals are observed for all protons in methyl 12-hydroxystearate, although in some cases several proton signals overlap. Presented in part at the JOCS-AOCS Joint Meeting, Los Angeles, April 1972.