首页 | 本学科首页   官方微博 | 高级检索  
相似文献
 共查询到20条相似文献,搜索用时 0 毫秒
1.
By 1,4-addition of arylaldehydes to 2,3-dimethyl-1,3-butadiene in the presence of sulfuric acid 2-aryl-4,5-dimethyl-3,6-dihydro-2H-pyrans are obtained. From 1,3-butadiene and isoprene beside the corresponding 3,6-dihydro-2H-pyrans by reaction with two more molecules aldehydetrans-2,4,7-triphenyl-4a,7,8,8a-tetrahydro-4H,5H-pyrano[4,3-d-1,3-dioxines are formed. With 1,3-cyclohexadiene, however, 1,2-addition of benzaldehyde is observed to givecis-r-2,c-4-diphenyl-4a,5,6,8a-tetrahydro-1,3-benzodioxane.

Herrn Prof. Dr.Anton v. Wacek, emerit. Vorstand des Instituts für Organische Chemie und Organisch-chemische Technologie der Technischen Universität Graz, in Verbundenheit zum 80. Geburtstag gewidmet.

1. Mitt.:H. Griengl undK. P. Geppert, Mh. Chem.107, 421 (1976).  相似文献   

2.
By reaction of excess benzaldehyde with cyclohexene in presence of sulfuric acid besider-2,c-4-diphenyl-(t-4aH,c-8aH)-hexahydro-4H-1,3-benzodioxin (2) andr-4-phenyl-(t-4aH,c-8aH)-hexahydro-4H-1,3,2-benzodioxathiin-2,2-dioxide (3),trans-2-benzyloxycyclohexyl phenyl ketone (5) and (E)-3-benzylidene-1-cyclohexenyl phenyl ketone (6) are obtained. The formation of5 and6 is shown to proceed via an acid catalyzedCannizzaro reaction of benzaldehyde.

2. Mitt.:H. Griengl undK. P. Geppert, Mh. Chem.107, 675 (1976).  相似文献   

3.
Summary 8a-Methoxy-3,4-dihydro-2H-1,4-benzoxazin-6(8aH)-ones2 undergo regio- and stereospecific 1,3-dipolar cycloaddition reactions with diazomethane or diazoethane to yield 3,4,6a,9,9a,9b-hexahydro-pyrazolo[3,4-h][1,4]benzoxazin-6(2H)-ones3, which slowly isomerize in solution to give the 3,4,8,9,9a,9b-hexahydro-pyrazolo[3,4-h][1,4]benzoxazin-6(2H)-ones5. The carbon of the diazoalkane dipole is attached to carbon C-8 of the benzoxazinone. The structures of the obtained products were determined by1H- and13C-NMR spectroscopy. An X-ray crystal structure analysis of3 a was carried out at room temperature:C11H15N3O3,M r =237.26, orthorhombic, Pc21n,a=9.173 (5),b=9.133 (4),c=13.281 (6),V=1112.6 (9) Å3,Z=4,d x =1.416 g/cm–3, =0.93 cm–1,R=4.33%,R w =3.95% (919 observations, 168 parameters).
Herrn Prof. Dr. W. Fleischhacker zum 60. Geburtstag gewidmet  相似文献   

4.
The four diastereomeric 2-(hydroxyphenylmethyl)cyclohexanols2a-2d are prepared. By reaction with benzaldehyde each2a-2c gives stereospecifically only one of the two possible configurationally correlated 2,4-diphenylhexahydro-4H-1,3-benzodioxins3a-3c. However, from (1RS, 2SR)-2 [(SR)-hydroxyphenylmethyl]cyclohexanol (2d) both dioxins3d and3e are obtained. The configurational assignments are based on1H-NMR spectroscopy and synthetic correlations. Conformational aspects are discussed. As is shown by chromatography, inPrins reactions of cyclohexene with benzaldehyde only one dioxin3c is formed.  相似文献   

5.
Trimethylsilylacetamide and trimethylsilyltrifluoroacetamide react with halogenodiorganylboranes to monomeric or dimeric amidoboranes depending on the organyl substituents. The compounds were characterized analytically and spectroscopically (NMR:1H,19F,11B; MS; IR).
21. Mitt.:A. Meller, W. Maringgele, K. Hennemuth undU. Sicker, J. Z. anorg. allg. Chem., im Druck.  相似文献   

6.
The syntheses of 4-amino-thiomorpholine-1,1-dioxide (12) and 4-hydroxythiomorpholine-1,1-dioxide (11) from 1,4-thioxane-1,1-dioxide (1) by pressureless reaction of1 with hydrazine hydrate and hydroxylamine, resp. is described. In analogy various other N-substituted thiomorpholine-1,1-dioxides are obtained with prim. amines (2–8) and diamines (9, 10).12 condensates with aldehydes (14–24) and ketones (25–29); reaction of12 with1 gives N,N-dithiomorpholine-1,1-dioxide (13). Acylation of12 with monochlorides (30–35), dichlorides of dicarboxylic acids (36–40) and carboxylic acid anhydrides (41–43) proceeds smoothly. Compounds38–43 are cyclic imides. Isocyanates give with12 the expected compounds45–48.12 reacts with chlorinated 1,3,5-triazines to compounds which can be purified only with difficulty (49–51). Quaternization of the N-substituted thiomorpholine-1,1-dioxides with benzylbromide (52, 53) and methyliodide (54, 55) is possible. Ethylenbromide reacts with9 to give the bis quaternization product56. Further reactions of thiomorpholine-1,1-dioxide (57) with sulfuryl chloride (58), bromo cyanide (59), allylic chloride (60), chloro acetonitrile (61) and trityl chloride (62) are described.11 reacts with carboxylic acid chlorides (63–65) and iso-cyanates (66–70) to yield the expected compounds. Propylene oxide gives with12 the addition product71; sulfur dioxide is added to11 to thiomorpholine-1,1-dioxide sulfonic acid (72).
Teil der Diplomarbeit vonMartin Irmgard, Technische Hochschule Aachen. 1975.  相似文献   

7.
The reaction of galliumtrichloride and galliumtribomide resp. with 2,6-dimethyl- and 2,4,6-trimethyl-N-trimethylsilyl-trifluoroacetanilide leads to the trifluoracetanilidodihalogenogallanes1–3. The 2,6,9-trioxa-4,8-diaza-1,5-digalla-bicyclo-[3.3.1]-nonadiene derivatives1 a–3 a are formed probably as by products.N-Trimethylsilyltrifluoroacetamide reacts with galliumtrichloride to yield the trifluoroacetamido-dichlorogallane4.N-Trimethylsilyl-N,N,N-triorganyl-thioureas react with galliumtrichloride under elimination of chlorotrimethylsilane to give the thio-ureido-gallanes5 and6. IfN,N-diorganylureas andN,N-diorganyl-thio-ureas resp. are reacted with galliumtrichloride and methyl-gallium-dichloride resp., the thio-ureido- and ureido-gallanes7–9 are obtained by elimination of hydrogenchloride. The compounds are characterized by analysis and spectral data (NMR:1H,19F; MS; IR). The substances are monomeric in the gas phase, obviously due to internal coordination.
30. Mitt.:W. Maringgele undA. Meller, J. Organomet. Chem., im Druck.  相似文献   

8.
A widely applicable method for the preparation of chelating resins based on glucose- and sucrosemethacrylate-gels is described. Primary aromatic amino groups were bonded to the carrier by esterification with 4-nitrobenzoylchloride and subsequent reduction of the nitro groups with sodium dithionite. Diazotation and coupling with various chelating ligands (8-hydroxyquinoline, dithizone, anthranilic acid, salicylic acid and pyrogallol) afforded chelating resins with capacities of max. 1.7 mmol/g. Sucrosemethacrylate-gels were etherified with 4-nitrobenzylchloride, epichlorohydrin, 4-nitrophenyl glycide ether (IIb), acrylonitrile and 4-nitrophenylacrylamide (IVb). Reaction of the gels with IIb or IVb and subsequent reduction of the nitro groups yielded reactive carriers with ether-linked primary aromatic amino groups. Diazotation and coupling with 8-hydroxyquinoline yielded chelating resins. The capacities of the gels were 0.6–0.7 mmol/g and these resins were extremely stable to changes inpH.
  相似文献   

9.
The synthesis of new hydrophilic polymer carriers on the basis of glucose-and sucrosemethacrylates is described. The monomer mixtures were prepared by reaction of glucose or sucrose with methacrylic anhydride or methacry-loylchloride in pyridine and by transesterification of sucrose with methylmethacrylate. Mixtures of methacrylic esters of glucosides could be obtained by analogous reaction of glucosides with methylmethacrylate. Radical polymerisation of the resulting mixtures of mono-and polyfunctional methacrylic esters of glucose and sucrose yielded crosslinked hydrophilic gels, swellable in water and polar organic solvents. The degree of crosslinking is determined by the ratio of mono- to polyfunctional esters in the monomer mixture, which depends on the molar ratio of reactants in the starting mixture. These neutral reactive carriers are stable to changes inpH and to biological degradation.
  相似文献   

10.
Addition of amines to dibenzylidene sulfamide1 a yields the correspondingSchiff bases3 a, b and monobenzylidene sulfamide2. Reaction of several dibenzylidene sulfamides1 with various lithium-amides gives N1-substituted N2-benzylsulfamoyl-benzamidines7 a-k via an intramolecular hydride transfer reaction, whereas by treatment of1 a with sodium amide 2-benzyl-3,5-diphenyl-3,4-dihydro-2H-1,2,4,6-thiatriazine-1,1-dioxide8 is obtained, which on hydrolysis yields9 and11. Alkylation products are described, the isomeric products12a/13a and12b/13b are isolated, their structures are confirmed by synthesis, IR and NMR-spectra.
  相似文献   

11.
The reaction of trimethylsilylcarbonamides with halogeno-diorganyl-boranes resp. trihalogenoboranes or organodihalogenoboranes gives monomeric resp. dimeric amidoboranes (borylcarbonamides) and derivatives of 4,8-diaza-1,5-dibora-2,6,9-trioxabicyclo[3.3.1]nonadienes. By reaction of the free acylamides with halogenoboranes in most cases the imide halides could be isolated as the only products. By reaction of the hydrochloride of bis(dimethylamino)-hydroxyborane withn-butyl-lithium followed by addition of the imide halides, the corresponding imidoylamines were formed.1H,11B, and19F-nmr spectra, mass spectra and characteristic ir group frequencies are reported.
15. Mitt.:W. Maringgele undA. Meller, Z. anorg. allg. Chem., im Druck.  相似文献   

12.
Thiomorpholine as well as alkyl substituted thiomorpholines and their Sdioxides, respectively, are transformed into the corresponding N-Aminothiomorpholines by nitrosation (1–5) followed by the reduction with zinc in acetic acid/acetic acid anhydride under simultaneous formation of the corresponding N-acetyl derivates, and hydrolysis by hydrochloric acid (6–9). Examples of this method are described. 4-Aminothiomorpholines and their Sdioxides react with aldehydes or ketones to give azomethines (10–31). Acylation with mono-and dicarbonic acid chlorides leads to the N-acyl derivatives32–44.Mannich condensation is also possible. By oxidation with yellow mercury oxide tetracenes are formed (46–47).
Teil der DissertationM. Schmitz, Techn. Hochschule Aachen, 1975.  相似文献   

13.
Reaction of the betaine1 and pyridinebetaine8 with trifluoroacetic anhydride yields the salts4a or9a and the yellow ylide5, respectively. In an analogous manner8 reacts with trichloroacetic anhydride to give11a. In a competitive reaction the trifluoroacetates6 and10 are also formed. Pyridinebetaine hydrochloride reacts similarily with trichloroacetic anhydride.
12. Mitt.:Wittmann H., Sobhi D., Petio F. A., Z. Naturf.31 b, 850 (1976).  相似文献   

14.
Summary Thep-benzoquinones5e-j react with diazomethane (after dehydrogenation) to 6-anilino-2e, dimethylamino-2h, phenylthio-2i, and methylthioindazolquinone2j. Methylation with dimethylsulfate of these as well as of the already known indazolquinones 6-toluidino-2f, 6-methylanilino-2g, 5-tert.butyl-2m, 5,6-methyl- (isomer mixture)2l,n, and benz-indazolquinone2o yield the 1-and 2-N-methyl derivatives3 and4. The structure of the 2-methyl derivatives is established by reaction of the corresponding benzoquinones with 3-methylsydnon in the case of4e,4g. UV/VIS-, IR- and1H-NMR-spectroscopy (in CDCl3 andDMSO) were used for structure determination. Comparison of the UV/VIS-spectra of2–4 shows that the indazolquinones are existing as 2 H-4,7-diones. For the structure elucidation of the 1- rs. 2-methylderivatives (whichh can be attributed to the methylation products) NMR-spectroscopy is well suited even without knowing the second isomer (solvent-effect). The course of the reaction of quinones with diazomethane and of the methylation reactions of the indazolquinones is discussed.
Herrn Univ.-Prof. Dr. G. Zigeuner zum 70. Geburtstag gewidmet  相似文献   

15.
By 1,4-addition of arylaldehydes to 2,3-dimethyl-1,3-butadiene in the presence of sulfuric acid 2-aryl-4,5-dimethyl-3,6-dihydro-2H-pyrans are obtained. From 1,3-butadiene and isoprene beside the corresponding 3,6-dihydro-2H-pyrans by reaction with two more molecules aldehydetrans-2,4,7-triphenyl-4a,7,8,8a-tetrahydro-4H,5H-pyrano[4,3-d-1,3-dioxines are formed. With 1,3-cyclohexadiene, however, 1,2-addition of benzaldehyde is observed to givecis-r-2,c-4-diphenyl-4a,5,6,8a-tetrahydro-1,3-benzodioxane.  相似文献   

16.
Summary 3,4-Dihydro-8a-methoxy-2H-1,4-benzoxazin-6(8aH)-ones — quinol derivatives of 2-hydroxyethylamino-1,4-benzoquinones — react with diazoalkanes to yield 2,3,9a,9b-Tetrahydro-9H-pyrazolo[3,4-h]-1,4-benzoxazin-6(6aH)-ones (3). Their structures were established on basis of NMR-techniques including two-dimensional experiments. The orientation phenomena of the reaction is discussed.
  相似文献   

17.
Zusammenfassung Der Vorgang der thermischen Umlagerung des 4-Hydroxy-5-acetyl-6-phenyl-pyrons-(2) (1) zum 4-Hydroxy-5-benzoyl-6-methyl-pyron-(2) (4) wird an Hand weiterer Beispiele studiert und ferner der Einfluß der Substituenten am C-5 bzw. C-6 des Lactonringes untersucht.
An investigation of more examples of the thermal rearrangement of 5-acetyl-4-hydroxy-6-phenyl-pyrone-(2) to 5-benzoyl-4-hydroxy-6-methyl-pyrone-(2) was carried out, it showed the influence of substituents at C-5 and C-6 of the lactone ring.
  相似文献   

18.
Starting with the chloromethyl compounds7 the new 2-azidomethyl-3-aryl-4-quinazolinones8 a-h were prepared, some of which have been reduced so far to the corresponding amines9 a, b, e, g by H2S in good yield. As a first example for the capability of the azides8 to undergo 1,3-dipolar cycloaddition the 2-quinazolinmethyl-1,2,3-triazol-4,5-dicarboxylicacid dimethylesters11 b, e, g were prepared by reacting8 with dimethylacetylenedicarboxylate (10).
1. Mitt.:Domanig R., Arch. Pharm., im Druck.  相似文献   

19.
Two further aporphine alcaloids, N-methyllaurotetanine and boldine, were used to the synthesis of aristolochic acid analogs. By means of their destruction and nitration of the reaction products two new nitrophenanthrene acids were obtained and their chemical structures were proved.
  相似文献   

20.
Reaction of the vicinal diols of steroids1, 5, 7, 10, 13, and16 with TPP/DEAD yields both regio-and stereospecifically the oxosteroids2, 6, 8, 11, 14, and15 by displacement of an axial hydrogen and extrusion ofTPPO besides the cholest-4-en-6-ols9 and12 and the cyclic carbonate3. 16, 17-androstandiol16 gives only the cyclic carbonate17. The different structures of the carbohydrates withcis-diol arrangement19 and21 lead exclusively to cyclic carbonates20 and22 in moderate yields. Treatment of1 with TPP/DEAD/HN3 affords 3-azido-2-hydroxycholestane4 in addition to the above mentioned2.
  相似文献   

设为首页 | 免责声明 | 关于勤云 | 加入收藏

Copyright©北京勤云科技发展有限公司  京ICP备09084417号