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1.
《Journal of Inorganic and Nuclear Chemistry》1979,41(8):1223-1227
The amine- and diamine-cyanoboranes, amine·nBH2CN (n = 1, amine = O(CH2CH2)2NMe and Me2NCH2CH2CN; n = 2, amine = Me2NCH2CH2NMe2 and H2NCH2CH2NH2) were prepared from the amine hydrochlorides and NaBH3CN. New amine- and diamine-carboxyboranes, amine·nBH2COOH(n = 1, amine = C5H5N and O(CH2CH2)2NMe; n = 2, amine = Me2NCH2CH2NMe2) were prepared by alkylation of the corresponding amine-cyanoborane with Et3OBF4 to the N-ethylnitrilium salts and subsequent reaction with water. In one case hydrolysis with NaOH resulted in the bis (N-ethylamidoborane), (Me2NCH2CH2NMe2)·2BH2C(O)NHEt. Preliminary results of studies of antitumor, and hypocholesterolemic activity in mice of several of these compounds are reported. 相似文献
2.
超声波技术制备功能化二氧化硅在苯酚和碳酸二甲酯甲基化反应中的应用 总被引:1,自引:0,他引:1
Porous silica modified with -(CH2)3NH2 (primary amine), -(CH2)3NHCH2CH2NH2 (secondary/primary amine) and -(CH2)3N-cycl-(CH2)4 (tertiary amine) were synthesized by ultrasonic technique under mild conditions. The samples were characterized by BET, elemental analysis and TG, showing that the organosilane moieties were grafted onto the surface of porous silica by covalent bond. The structure of the organosilane moieties and ultrasonic treatment time were all significant for the quantities of grafted amino groups. The samples exhibited promising catalytic properties towards the methylation reaction of phenol with dimethyl carbonate (DMC). The methylation reaction with the modified samples featured high selectivity at high conversion. The samples were subjected to utilization for a few recycles without obvious loss of activity to indicate that ultrasonic technique was effective for the preparation of organically modified porous silica catalysts. 相似文献
3.
Ibrahim Abdul Razak S. Shanmuga Sundara Raj Hoong‐Kun Fun Ye‐Xiang Tong Zhong‐Lin Lu Bei‐Sheng Kang 《Acta Crystallographica. Section C, Structural Chemistry》2000,56(3):291-292
In the crystal structure of the title compound, [Zn(C4H13N3)2]2[Fe(CN)6]·4H2O, the asymmetric unit is formed by a [Zn(dien)2]2+ cation (dien = diethylenetriamine, NH2CH2CH2NHCH2CH2NH2), water molecules and half of the [Fe(CN)6]4? anion which is related by inversion symmetry through the Fe atom. The geometry around the Zn and Fe atoms is distorted octahedral and octahedral, respectively. Intramolecular O—H?O hydrogen bonds involving the water molecules, and intermolecular O—H?N hydrogen bonds involving the water molecules and the anions, result in an infinite chain. Intramolecular O—H?O and N—H?N, and intermolecular O—H?N, N—H?O and N—H?N hydrogen bonds form a three‐dimensional framework. 相似文献
4.
Keypour Hassan Salehzadeh Sadegh Pritchard Robin G. Parish Richard V. 《Transition Metal Chemistry》2002,27(7):720-723
In the presence of copper(II) ion, two asymmetrical tripodal tetraamine ligands N{(CH2)3NH2}{(CH2)2NH2}2 (pee), N{(CH2)3NH2}2{(CH2)2NH2} (ppe) and one symmetrical ligand, N{(CH2)3NH2}3 (tpt), were condensed with 2-acetylpyridine. In EtOH–H2O solutions the reaction stops after the first condensation stage, and complexes of acyclic pentadentate(N5) mono-Schiff-base ligands were obtained. With asymmetrical tetraamines there are two possible condensation sites: the primary amine of the propylene, or the ethylene chain. The X-ray structure analysis of one complex, [Cu(ppe-py)](ClO4)2, indicates that condensation with 2-acetylpyridine in this case occurs at the propylene chain and the geometry around the copper ion is trigonal-bipyramidal. 相似文献
5.
Summary Aquocomplexes of copper(II) and nickel(II) involving (H2NCH2)2, H2NCH2CH2NHCH2CH2NH2 and H2NCH2CH2NHCH2CH2NHCH2CH2NH2 as ligands were prepared and characterised. Using a pH-stat method, the kinetics of the base hydrolysis of amino acid esters such as H2NCH2CO2CH3·HCl (GE), (HO)C6H4CH2-(NH2)CO2CH3·HCl (TE), CH3S(CH2)2CH(NH2)CO2CH3· HCl (ME), HSCH2CH(NH2)CO2C2H5·HCl (CE),
(HE) and [—SCH2CH(NH2)CO2CH3]2·2HCl (CysE) was studied. These complexes substantially enhance the rate of hydrolysis, the values of the second-order rate constants being some 10–30 times greater than those obtained in the presence of simple metal ions. 相似文献
6.
Robert J. Angelici Paul A. Christian B.Duane Dombek George A. Pfeffer 《Journal of organometallic chemistry》1974,67(2):287-294
The relative reactivities of CO and CNR ligands with CH3NH2 were investigated in complexes which contained both ligands. Like (C5H5Fe(CO)3+; the (C5H5)Fe(CO)2(CNCH3)+ complex reacts with CH3NH2 to give the carbamoyl complex (C5)Fe(CO)(CNCH3)(CONHCH3); this is a readily reversible reaction. In contrast, (C5H5)Fe(CO)(CNCH3)2+ reacts with CH3NH2 to give the amidinium or carbene complex, (C5H5)Fe(CO)(CNCH3)[C(NHCH3)2]+]. In a slow reaction, (C5H5)Fe(PPh3)(CO)(CNCH3)+ forms the amidinium complex, (C5H5)Fe(PPh3)(CO)[C(NHCH3)2]+. Factors that affect the site of CH3NH2 reaction are discussed. The complexes have been characterized by IR and NMR spectroscopy; a variable temperature NMR study of (C5H5)Fe(CO)(CNCH3)[C(NHCH3)2]+ indicates restricted rotation around the CN bonds of the amidinium ligand. 相似文献
7.
A general synthetic strategy for the preparation of polyazamacrocycles containing long aliphatic chains is reported. These compounds are 22- or 24-membered hexaazamacrocycles incorporating two diethylenetriamine subunits (H2NCH2CH2NHCH2CH2NH2) linked together either by two CH2CH2OCH2CH2 (see 4–6 ), two tetramethylene (see 7 ), or two pentamethylene (see 8 ) fragments. Whereas for compound 4 , one of the centrally located amine functionalities of the triamine subunit bears a hexadecyl chain, for compound 5 , two of such chains are centrally attached to both subunits. In macrocycles 6–8 , all six amino functionalities bear hexadecyl chains. Compounds 4–8 are potential candidates for the construction of selective chemical sensors such as specific electrodes for adenosine mono-, di-, and tri-phosphate. They may also be used for nucleoside polyphosphates extraction and/or transport. 相似文献
8.
Herbert Schumann Sebastian Dechert Frank Girgsdies Bernd Heymer Markus Hummert Ji‐Young Hyeon Jens Kaufmann Stefan Schutte Sonja Wernik Birgit C. Wassermann 《无机化学与普通化学杂志》2006,632(2):251-263
Synthesis and Characterization of New Intramolecularly Nitrogen‐stabilized Organoaluminium‐ and Organogallium Alkoxides The intramolecularly nitrogen stabilized organoaluminium alkoxides [Me2Al{μ‐O(CH2)3NMe2}]2 ( 1a ), Me2AlOC6H2(CH2NMe2)3‐2,4,6 ( 2a ), [(S)‐Me2Al{μ‐OCH2CH(i‐Pr)NH‐i‐Pr}]2 ( 3a ) and [(S)‐Me2Al{μ‐OCH2CH(i‐Pr)NHCH2Ph}]2 ( 4 ) are formed by reacting equimolar amounts of AlMe3 and Me2N(CH2)3OH, C6H2[(CH2NMe2)3‐2,4,6]OH, (S)‐i‐PrNHCH(i‐Pr)CH2OH, or (S)‐PhCH2NHCH(i‐Pr)CH2OH, respectively. An excess of AlMe3 reacts with Me2N(CH2)2OH, Me2N(CH2)3OH, C6H2[(CH2NMe2)3‐2,4,6]OH, and (S)‐i‐PrNHCH(i‐Pr)CH2OH producing the “pick‐a‐back” complexes [Me2AlO(CH2)2NMe2](AlMe3) ( 5 ), [Me2AlO(CH2)3NMe2](AlMe3) ( 1b ), [Me2AlOC6H2(CH2NMe2)3‐2,4,6](AlMe3)2 ( 2b ), and [(S)‐Me2AlOCH2CH(i‐Pr)NH‐i‐Pr](AlMe3) ( 3b ), respectively. The mixed alkyl‐ or alkenylchloroaluminium alkoxides [Me(Cl)Al{μ‐O(CH2)2NMe2}]2 ( 6 ) and [{CH2=C(CH3)}(Cl)Al{μ‐O(CH2)2NMe2}]2 ( 8 ) are to obtain from Me2AlCl and Me2N(CH2)2OH and from [Cl2Al{μ‐O(CH2)2NMe2}]2 ( 7 ) and CH2=C(CH3)MgBr, respectively. The analogous dimethylgallium alkoxides [Me2Ga{μ‐O(CH2)3NMe2}]2 ( 9 ), [(S)‐Me2Ga{μ‐OCH2CH(i‐Pr)NH‐i‐Pr}]n ( 10 ), [(S)‐Me2Ga{μ‐OCH2CH(i‐Pr)NHCH2Ph}]n ( 11 ), [(S)‐Me2Ga{μ‐OCH2CH(i‐Pr)N(Me)CH2Ph}]n ( 12 ) and [(S)‐Me2Ga{μ‐OCH2(C4H7NHCH2Ph)}]n ( 13 ) result from the equimolar reactions of GaMe3 with the corresponding alcohols. The new compounds were characterized by elemental analyses, 1H‐, 13C‐ and 27Al‐NMR spectroscopy, and mass spectrometry. Additionally, the structures of 1a , 1b , 2a , 2b , 3a , 5 , 6 and 8 were determined by single crystal X‐ray diffraction. 相似文献
9.
Kathleen M. Wollyung Chrys Wesdemiotis Andras Nagy Joseph P. Kennedy 《Journal of polymer science. Part A, Polymer chemistry》2005,43(5):946-958
This article reports the facile synthesis of novel terminally and centrally functionalized polyisobutylenes (PIBs) and the detailed characterization of the products by various mass spectrometry techniques. Specifically, H? PIB? CH2? C(OH)CH3? CH2? NHCH3 and [H? PIB? CH2? CH(OH)CH3? CH2]2? NCH3 were synthesized by the quantitative epoxidation of H? PIB? CH2? C(CH3)?CH2 and the subsequent conversion of the resulting epoxide with excess CH3NH2. Quaternization with CH3Cl of these mixtures of secondary and tertiary amines yielded exclusively H? PIB? CH2? C(OCH3)CH3? CH2? N(CH3)2 from the secondary amine, whereas the tertiary (centrally functionalized) amine remained unchanged. Tandem mass spectrometry experiments provided unique insight into the precise connectivity of the functional end groups added to the PIB frame. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 946–958, 2005 相似文献
10.
The kinetics of the base catalysed racemization of [Co(EN3A)H2O] 1 Abbreviations: EN3A3?=(?OOCCH2)2N(CH2)2NHCH2COO?; ME3A3?=(?OOCCH2)2N(CH2)2 N(CH3)CH2COO?; EDDA2?=?OOCCH2NH(CH2)2NHCH2COO?; EDTA4?=(?OOCCH2)2N(CH2)2N(CH2COO?)2;TNTA4?=(?OOCCH2)2N(CH2)3N(CH3COO?)2; HETA3?=(?OOCCH2)2N(CH2)2N(CH2COO?)CH2CH2OH; en=H2N(CH2)2NH2; Meen=H2N(CH2)2NHCH3; sar?=?OOCCH2NHCH3. were studied polarimetrically in aqueous buffer solution. The reaction rate is first order in OH? and in complex, in weakly acidic medium. Activation parameters are ΔH≠=22 kcal · mol?1, ΔS≠=26 cal · K?1. The results are discussed in terms of an SN1CB mechanism involving exchange of the ligand water molecule. The N-methylated analogue [Co(ME3A)H2O] does not racemize in the pH-range investigated. Loss of optical activity occurs at a rate which is about 1,000 times slower than the racemization of [Co(EN3A)H2O](60°) and coincides with the decomposition of the complex. 相似文献
11.
Summary Aquocomplexes of cobalt(II), cobalt(III), palladium(II) and platinum(II) involving (H2NCH2)2, [H2N(CH2)2]2NH and [H2N(CH2)2NHCH2]2 as ligands were prepared and characterized. The kinetics of base hydrolysis of the amino acid esters H2NCH2CO2Me·HCl, HOC6H4CH2CH (NH2)CO2Me·HCl, MeS(CH2)2CH(NH2)CO2Me·HCl, HSCH2CH(NH2)CO2Et·HCl, C3H3N2CH2CH(NH2)-CO2Me·2HCl and [—SCH2CH(NH2)CO2Me]2·2HCl in the presence of these complexes have been studied. The rate of hydrolysis is influenced substantially by these complexes and the second order rate constants are some 10–90 times greater than those obtained in the presence of simple metal ions. 相似文献
12.
Treatment of perfluoro-n-octanonitrile with phenylphosphine gave tetraphenyltetraphosphine and a spectrum of reduction and interaction products. Fifteen compounds were identified. The imine, (RfC7F15) RfCHNH, and the amine, RfCH2NH2, were the primary reduction products. Secondary phosphorus-free products, some formed following ammonia evolution, were the following: RfCHNCH2Rf, RfCH2CH(NH2)Rf, RfC(NH)NCRf(NH2), RfCH2NHCRf(NH), (RfCN)3, RfCHNCRfNCRf(NH), RfCH2NCRfNHCH2Rf, and RfCH2NCRfNHCRf(NH). Only three phosphorus-containing materials were definitely identified: RfCH(NH2)P(C6H5)H, RfCH[P(C6H5)H]NCHRf, and RfC(NH)P(C6H5)CRf(NH). Depending on reaction conditions, specific phosphorus-containing compounds could be preferentially produced. All the structure assignments are based solely on mass spectral breakdown patterns, since pure compounds were not isolated. 相似文献
13.
《Journal of organometallic chemistry》1986,316(3):C21-C23
Metallation of the ynamine CH3CCNEt2 or the allenic amines H2CCCHNR2 (R = CH3 or C2H5) with Schlosser's reagent BuLi · t-BuOK, followed by reaction with a thiocarbonyl compound XCSSCH3 (X = Me2N, Et2N, CH3S, t-Bu, O-t-Bu, Ph or 2-thienyl) and then addition of water, gives 2,5-disubstituted thiophenes (with Me2N or Et2N and X as substituents) in good yields. 相似文献
14.
Khodayar Gholivand Zahra Hosseini Mehrdad Pourayoubi Zahra Shariatinia 《无机化学与普通化学杂志》2005,631(15):3074-3079
Some new N‐carbonyl, phosphoramidates with formula C6H5C(O)N(H)P(O)R2 (R = NC3H6 ( 1 ), NC6H12 ( 2 ), NHCH2CH=CH2 ( 3 ), N(C3H7)2 ( 4 )) and CCl3C(O)N(H)P(O)R′2 (R′ = NC3H6 ( 5 ), NHCH2CH=CH2 ( 6 )) were synthesized and characterized by 1H, 13C, 31P NMR and IR spectroscopy and elemental analysis. The structures were determined for compounds 1 and 2 . Compound 1 exists as two crystallographically independent molecules in crystal lattice. Both compounds 1 and 2 produced dimeric aggregates via intermolecular ‐P=O…H‐N‐ hydrogen bonds, which in compound 2 is a centrosymmetric dimer. In compounds with four‐membered ring amine groups, 3J(P,C)>2J(P,C), in agreement with our previous studies about five‐membered ring amine groups. Also, 3J(P,C) values in compounds 1 and 5 are greater than in compounds with five‐, six‐ and seven‐membered ring amine groups. 相似文献
15.
《Journal of solid state chemistry》1987,71(2):451-457
The intercalation of alkyl diamines in the protonic oxide HNb3O8 · H2O is quantitative for the diamines H2N(CH2)nNH2 with n ranging from 2 to 10. All the intercalated oxides [H3N(CH2)nNH3]0.5Nb3O8 · yH2O are hydrated at room temperature; they can be easily and reversibly dehydrated to the oxides [H3N(CH2)nNH3]0.5Nb3O8. The structural behavior of those compounds is compared to that of the alkyldiammonium titanoniobates [H3N(CH2)nNH3]0.5TiNbO5. An interpretation of their structural properties is given which takes into account the tendency of amines to assume an orientation transverse to oxide layers, the conformation of the amine chains, and the tendency to form dense organic layers. 相似文献
16.
Toschitake Iwamoto 《Journal of inclusion phenomena and macrocyclic chemistry》1996,24(1-2):61-132
One-, two- and three-dimensional CN-bridged metal complex structures made up of building blocks such as linear [Ag(CN)2]–, square planar [Ni(CN)4]2– or tetrahedral [Cd(CN)4]2–, and of the complementary ligands such as ammonia, water, unidentate amine, bidentate a,w- diaminoalkane, etc., are reviewed with an emphasis on their behaviour as hosts to afford clathrate inclusion compounds with guest molecules and as self-assemblies to form supramolecular structures with or without guests. The historical background is explained for Prussian blue and Hofmann's benzene clathrate based on their single crystal structure determinations. The strategies the author and coworkers have been applying to develop varieties of clathrate inclusion compounds from the Hofmann-type are demonstrated with the features observed for the developed structures determined by single crystal X-ray diffraction methods.Abbreviations for Ligands and Guests mma
NMeH2
- dma
NMe2H
- tma
NMe3
- mea
NH2(CH2)2OH
- en
NH2(CH2)2NH2
- pn
NH2CHMeCH2NH2
- tn
NH2(CH2)3NH2
- dabtn
NH2(CH2)4NH2
- daptn
NH2(CH2)5NH2
- dahxn
NH2(CH2)6NH2
- dahpn
NH2(CH2)7NH2
- daotn
NH2(CH2)8NH2
- danon
NH2(CH2)9NH2
- dadcn
NH2(CH2)10NH2
- mtn
NMeH(CH2)3NH2
- dmtn
NMe2(CH2)3NH2
- detn
NEt2(CH2)3NH2
- temtn
NMe2(CH2)3NMe2
- dien
NH2(CH2)2NH(CH2)2NH2
- pXdam
p-C6H4(NH2CH2)2
- rnXdam
m-C6H4(NH2CH2)2
- py
C5H5N pyridine
- ampy
NH2C5H4N aminopyridine
- Clpy
CIC5H4N chloropyridine
- Mepy
MeC5H4N methylpyridine
- dmpy
Me2C5H3N dimethylpyridine
- bpy
NC5H4C5H4N bipyridine
- quin
C7H9N quinoline
- iquin
iso-C7H9N isoquinoline
- qxln
C8H6N2 quinoxaline
- Pe
C5H11-pentyl imH: C3N2H4 imidazole
- pyrz
N(CHCH)2N pyrazine
- Mequin
MeC7H8N methylquinoline
- bppn
C13H14N2 1,3-bis(4-pyridyl)propane
- bpb
C14H8N2 1,4-bis(4-pyridyl)butadiyne
- N-Meim
C3N2H3Me N-methylimidazole
- 2-MeimH
C3N2H3Me 2-methylimidazole
- dmf
HOCNMe2 dimethylformamide
- hmta
C6H12N4 hexamethylenetetramine
-
o-phen
C12H8N2 1,10-phenanthroline
- den
HN(CH2CH2)2NH piperazine
- morph
HN(CH2CH2)2O morpholine
- ten
N(CH2CH2)3N 1,4-diazabicyclo[2.2.2]octane
- ameden
NH2(CH2)2N(CH2CH2)2NH N-(2-aminoethyl)piperazine
Presented at the Sixth International Seminar on Inclusion Compounds, Istanbul, Turkey, 27–31 August, 1995. 相似文献
17.
《Tetrahedron》1988,44(9):2569-2574
Rate constants for the aminolysis of a few O-aryl oximes with several primary alkl amines, CH3NH2—C6H13NH2, in 1:1 water-acetonitrile are reported. Reactions of methylamine with substrates possessing poor nucleofugues are very weakly sensitive to base catalysis while reactions of higher amines are not. Slightly higher rate of long chain amine may be considered as a consequence of hydrophobic interaction. Cationic micelles of cetyltnmethyl ammonium bromide enhance the rate. Magnitude of micellar catalysis increases towards higher amines. 相似文献
18.
The Lewis base SMe2 in 7‐B11H13(SMe2) ( 1a ) can be replaced by the amines L = NH2(CH2tBu), NH2Cy, NH2Ph, NH2(4‐C6H4Me), py, chinoline or the phosphanes L = PPh3, PMePh2, yielding 7‐B11H13L ( 1b ‐ i ). The borane 1a can be deprotonated by certain amines, alkanides, or hydrides to give the anion 7‐B11H12(SMe2)‐ ( 2a ). Replacing the base SMe2 in the anion 2a by weak bases gives B11H12L‐ (L = PPh3, MeCN; 2h , j ). Upon reaction of 1a with the amine NH2(CH2tBu) in the ratio 1:2, a deprotonation and the substitution of SMe2 by the amine are observed, 7‐B11H12[NH2(CH2tBu)]‐ ( 2b ) being formed. At 170 °C, the 7‐isomers 1b , f are isomerized into a mixture of the corresponding 1‐ and 2‐isomers ( 1b′ , f′ and 1b″ , f″ , respectively). 相似文献
19.
Baranova O. V. Kosmynin V. V. Savelova V. A. Shendrik A. N. Korotkikh N. I. Raenko G. F. Popov A. F. 《Russian Journal of Organic Chemistry》2002,38(3):378-384
Onium salts QZ (Z = Cl, Br) having a lipophilic (Q = R3NR', where R' = C16H33) or readily extractable (into organic phase) cation (Q = Ph4P) exhibit a high catalytic activity in phase-transfer alkaline hydrolysis of N-benzyloxycarbonylglycine 4-nitrophenyl ester in the two-phase system chloroform-borate buffer (pH 10). No catalytic effect is observed in the presence of hydrophilic ammonium salts [Et4NCl, Et3PhCH2NCl, Me2(NH2)+NCH2CH2+N(NH2)Me2·2Br-] and those insoluble in organic solvents [(Me)3+NNH(CH2)2COO-·2H2O, Me2(NH2)+NCH2CO-, Me2(NH2)+N(CH2)3SO3
-]. These data suggest extraction mechanism of the process. The activity of lipophilic cation Q is determined mainly by two factors: its extractibility, on the one hand, and the ability to form micelles, on the other. 相似文献
20.
Helmut Fric Michael Puchberger Ulrich Schubert 《Journal of Sol-Gel Science and Technology》2006,40(2-3):155-162
The structural chemistry of crystalline adducts M2(OR)8(amine)2 (M = Ti: OR = OiPr, amine = NH2CH2Ph, NH2Bu; M = Ti: OR = OEt, amine = piperidine; M = Zr: OR = OiPr, amine = NH2CH2Ph, NH2C6H11) is discussed. The adducts were obtained by reaction of Ti(OEt)4 or M(OiPr)4 with primary or secondary amines. The monoamine adducts are centrosymmetric dimers in which the amines are coordinated axially
to the M2μ-OR)2 ring and hydrogen-bonded to neighboring alkoxo ligands. The adducts are sufficiently stable if the hydrogen bond is strong.
15N NMR studies revealed that the amines are also coordinated in solution. Coordination polymers were obtained when diamines
with two terminal NH2 groups are reacted with Ti(OiPr)4. The general structure is the same as that of Ti2(OiPr)8(RNH2)2. However, the diamines bridge the Ti2(OiPr)8 units. When Zr(OiPr)4 was reacted with NH2CH2CH2NHMe, the adduct Zr2(OiPr)8[NH2CH2CH2NHMe]2 was obtained where only the NH2 group is coordinated. 相似文献