共轭高分子的研究——Ⅶ.脂肪腈类的聚合

<正> 聚腈作为新的一类共轭高分子而引起注意。本文在前报的基础上进一步选择了一系列脂肪腈(乙腈、丙腈、戊腈、庚腈和苯乙腈),系统地研究它们在络合能力较强的付氏试剂(BF_3和TiCl_4等)作用下的聚合反应与机理,同时测定了各聚腈的物理性能。 1.腈的络合聚合 腈类与付氏试剂可形成定组成的络合物结晶:     

Efficient Hydroboration of Esters and Nitriles Using a Quinazolinone-Supported Titanium(IV) Multitasking Catalyst

We report catalytic hydroboration of esters as well as nitriles under solvent-free and mild conditions using single titanium(IV) metal complex, [{κ²-C₆H₄C(O)N(ⁱPr)C(N-ⁱPr)=N}{κ³-(ⁱPr)N=C(O)−C₆H₄−NC(NMe₂)N(ⁱPr)}TiNMe₂] 1 as a sustainable, economical, and efficient pre-catalyst. The molecular structure of the Ti^IV complex in the solid state reveals the unique coordination of Ti^IV metal with N, N, and O atoms of one quinazolinone unit via in-situ rearrangement, while another quinazolinone moiety coordinates in bidentate fashion via both N atoms only. The Ti^IV complex demonstrates excellent activity as a pre-catalyst towards the hydroboration of a wide array of esters and nitriles with pinacolborane (HBpin) to afford alkoxyboranes and diboryl amines in high yield (up to 99 %) with greater tolerance to a variety of electron-withdrawing and electron-donating functional groups. A most plausible mechanism of hydroboration of esters is also proposed based on kinetics and NMR studies, which suggests the formation of titanium-hydride species as an active catalyst.     

Solvent-Free Conversion of N,N-Dimethylhydrazones to Nitriles Under Microwave Irradiation

A variety of aldehyde N,N-dimethylhydrazones are rapidly converted into the corresponding nitriles using oxone supported on wet Al₂O₃ under microwave irradiation in dry media.     

TrocCl Mediated Efficient Synthesis of Nitriles from Primary Amides

In order to establish a rapid conversion method of primary amides to nitriles, various types of carboxamides were treated with 2,2,2-trichloroethyl chloroformate and Et₃N, as a dehydrating agent to obtain the desired nitriles in 82–95% yields.     

Rapid Method of Converting Primary Amides to Nitriles and Nitriles to Primary Amides by ZnCl2 using Microwaves under Different Reaction Conditions

A rapid and facile method for the conversion of primary amides to nitriles using inexpensive and readily available ZnCl₂ in aqueous acetonitrile and their regeneration using ZnCl₂–H₂O–THF in the presence of acetamide under microwave irradiation in good yields is reported. The reactions go to completion within a minute.     

Preparation of Polyfunctionalized Aromatic Nitriles from Aryl Oxazolines

A selective ortho,ortho’-functionalization of readily available aryl oxazolines by two successive magnesiations with sBu₂Mg in toluene followed by trapping reactions with electrophiles, such as (hetero)aryl iodides or bromides, iodine, tosyl cyanide, ethyl cyanoformate or allylic bromides (39 examples, 62–99 % yield) is reported. Treatment of these aryl oxazolines with excess oxalyl chloride and catalytic amounts of DMF (50 °C, 4 h) provided the corresponding nitriles (36 examples, 73–99 % yield). Conversions of these nitriles to valuable heterocycles are reported, and a tentative mechanism is proposed.     

Synthesis of Aromatic Nitriles Using Nonmetallic Cyano‐Group Sources

Aromatic nitriles are prepared efficiently through transition‐metal‐mediated cyanation of aryl (pseudo)halides with metallic cyano‐group sources, such as CuCN, KCN, NaCN, Zn(CN)₂, TMSCN, or K₄[Fe(CN)₆]. However, this approach often suffers from drawbacks, such as the formation of stoichiometric amounts of metal waste, the poisoning of the metal catalysts, or the generation of toxic HCN gas. As a result, a range of “nonmetallic” organic cyano‐group sources have been explored for the cyanation of aryl halides and arene C? H bonds. This Minireview summarizes types of nonmetallic cyano‐group sources and their applications in the preparation of aryl nitriles.     

Ruthenium-Catalyzed Deaminative Hydrogenation of Amino Nitriles: Direct Access to 1,2-Amino Alcohols

A new approach for the efficient and highly selective synthesis of 1,2-amino alcohols by direct reductive hydrolysis of N-formyl-protected α-amino nitriles is reported. The commercially available RuHCl(CO)(PPh₃)₃ complex was found to be a suitable catalyst for this operationally simple protocol, in which no stoichiometric amounts of undesired metal waste are generated. The deaminative hydrogenation is performed at 55 bar of H₂, using a 6:1 mixture of 1,4-dioxane/water as solvent. In addition, hydroxymethyl alcohols were prepared from cyanoketones under very similar conditions.     

Cyclization of Zincated α‐N‐Homoallylamino Nitriles: A New Entry to Enantiopure 2,3‐Methanopyrrolidines

Stereoselective cyclization of zincated α‐N‐homoallylamino nitriles has been developed. Following treatment with lithium diisopropylamide (LDA) and transmetalation with zinc bromide, α‐N‐(1‐phenylethyl)‐N‐homoallylamino nitriles lead to 2,3‐methanopyrrolidines in moderate to good yields (up to 66 %) and excellent selectivities (up to >98:2). With substrates derived from α‐branched homoallylic amines, a stereospecific inversion of the homoallylic stereogenic center was observed. To account for this, a mechanistic rationale involving the formation of zincioiminium ions from zincated α‐amino nitriles is put forward. 2,3‐Methanopyrrolidines should then arise from a sequence involving an aza‐Cope rearrangement providing a configurationally stable (2‐azoniaallyl)zinc species that then undergoes a [3+2] cycloaddition reaction.     

Trimethylsilylcyanation of Heterocyclic Aldimines - Derivatives of 2-Trifluoromethylaniline

The addition of trimethylsilyl cyanide to the CH=N bond of furan, thiophene, and pyridine azomethines in the presence of aluminum bromide as catalyst was studied. The effect of the CF₃ group in the aldimines produced by the condensation of O-, S-, and N-heteroaromatic aldehydes with 2-trifluoromethylaniline on the reaction and also other relationships of the investigated processes were studied. The corresponding furan, thiophene, and pyridine -amino nitriles were synthesized.     

Reactions of rac‐(ebthi)M(η2‐Me3SiC2SiMe3) (M=Ti,Zr) with Aryl Nitriles

The reactions of the Group 4 metallocene alkyne complexes rac‐(ebthi)M(η²‐Me₃SiC₂SiMe₃) ( 1 a : M=Ti, 1 b : M=Zr; rac‐(ebthi)=rac‐1,2‐ethylene‐1,1′‐bis(η⁵‐tetrahydroindenyl)) with Ph?C?N were investigated. For 1 a , an unusual nitrile–nitrile coupling to 1‐titana‐2,5‐diazacyclopenta‐2,4‐diene ( 2 ) at ambient temperature was observed. At higher temperature, the C?C coupling of two nitriles resulted in the formation of a dinuclear complex with a four‐membered diimine bridge ( 3 ). The reaction of 1 b with Ph?C?N afforded dinuclear compound 4 and 2,4,6‐triphenyltriazine. Additionally, the reactivity of 1 b towards other nitriles was investigated.     

Cyclotrimerization of Nitriles Catalyzed by SmI2/Amines: Synthesis of 2,4,6-Trisubstituted-S-Triazines

SmI₂ has been found to catalyze a reaction of cyclotrimerization of nitriles in the presence of amine as cocatalyst to give 2,4,6-trisubstituted-s-triazines effectively under mild reaction conditions. The yield depends on the structure of nitriles.     

Efficient Dehydration of Aldoximes to Nitriles with TiCl3(OTf)

Aromatic, alicyclic, olefinic as well as heterocyclic aldoximes, were dehydrated to their corresponding nitriles with 0.15 molar equivalents of TiCl₃(OTf) in sealed tube at 80°C in 85-97% yield.     

The Structure of Lithium Compounds of Sulfones,Sulfoximides, Sulfoxides,Thioethers and 1,3-Dithianes,Nitriles, Nitro Compounds and Hydrazones

Acceptor-substituted lithio compounds LiA? CR¹R², in which the acceptor A is an RC(0), N?C, RSO₂, RS(O)NR, RSO, RS, O₂N, or RC(N? NR₂) group, have long played an important role in organic synthesis. Their significance has grown still further in the last fifteen years, as one has increasingly learnt to employ them successfully in chemo-, regio-, diastereo-and enantioselective reactions. Remarkably, little if anything was known of the structures of these compounds. It is therefore not surprising that interest in the structures of this class of compounds has greatly increased in recent years. In the following review, we shall summarize recent research into the structures of the lithio compounds of sulfones, sulfoximides, sulfoxides, thioethers and 1,3-dithianes, nitriles, nitro compounds, and hydrazones. Crystal structure determinations from recent years are central to this study. They are supplemented by solution studies and by calculations of structures. Structural similarities and differences between the individual states of aggregation are pointed out wherever possible, as is also the relationship between structure and reactivity.     

Photocatalytic Conversion of Benzyl Alcohols/Methyl Arenes to Aryl Nitriles via H-Abstraction by Azide Radical

This report presents the visible-light-assisted synthesis of aryl nitriles from easily accessible alcohols or methyl arenes in the presence of O₂. Organic photoredox catalyst, 4CzIPN (1,2,3,5-tetrakis(carbazol-9-yl)-4,6-dicyanobenzene), induces single electron transfer (SET) from azide N₃⁻ and generates azide radical N₃⋅.The photogenerated N₃⋅ abstracts H atom from α-C−H bond of benzylic system, which provides aldehyde and hydrazoic acid (HN₃) in situ. This reaction subsequently forms azido alcohol intermediate that transforms into nitrile with the assistance of triflic acid (Brønsted acid). A range of alcohols and methyl arenes successfully underwent cyanation at room temperature with good to excellent yields and showed good functional group tolerance.     

The Addition of Nitriles to Tetramesityldisilene: A Comparison of the Reactivity between Surface and Molecular Disilenes

The addition of acetonitrile, propionitrile, and phenylacetonitrile to tetramesityldisilene (Mes₂Si?SiMes₂) was examined. In general, 1,2,3‐azadisiletines and the tautomeric enamines were formed, although a ketenimine was formed as the major product in the addition of phenylacetonitrile to the disilene. In the presence of LiCl, the mode of addition changed for both acetonitrile and propionitrile: insertion into the α‐CH bond of acetonitrile and/or formation of the formal HCN adduct was observed. Preliminary investigations of the reactivity of the nitrile adducts are also reported. A comparison between the reactivity of nitriles with Mes₂Si?SiMes₂ and the Si(100)‐2×1 surface was made both in terms of the types of adducts formed and their reactivity. Some insights into the surface chemistry are offered.     

Theoretical study of 1,3-dipolar cycloaddition of nitrones to doubly activated nitriles

The mechanism of 1.3-dipolar cycloaddition of nitrones (CH₂=N(CH₃)O) to doubly activated nitriles RCN has been comprehensively studied by theoretical quantum-chemical methods for the model compound trans-[PtCl₂(N≡CCH₃)(N≡CCF₃)] as an example. The reaction proceeds by a strongly asynchronous concerted mechanism through the formation of a five-membered cyclic transition state. Studying the effect of a solvent on the process shows that solvation effects inhibit cycloaddition. Double activation of RCN by introducing the electron-withdrawing substituents R = CF₃ followed by coordination to a transition metal is the most promising way to enhance the reactivity of nitriles in cycloaddition reactions.     

A Direct and Efficient Synthetic Method for Nitriles from Ketones

Cyclic cyano derivatives 3 were obtained by the reaction of Me₃SiCN / ZnI₂ with the cyclic ketones 2 which gave the trimethylsilyloxy nitriles 4. They were directly transformed to cyano derivatives 3 (70–80% yield) by the reductive reagent Me₃SiCl-NaI in acetonitrile in the presence of H₂O.     

Synthesis of α-amino nitriles through Strecker reaction of aldimines and ketoimines by using nanocrystalline magnesium oxide

Strecker reactions of various aldimines as well as ketoimines with TMSCN proceeded smoothly under mild conditions to give the corresponding α-amino nitriles and α,α-disubstituted α-amino nitriles, respectively, in good to excellent yields in the presence of nanocrystalline magnesium oxide. The reaction proceeds through hypervalent silicate species by coordination to O²⁻/O⁻ (Lewis basic site) of nanocrystalline magnesium oxide, proved by ²⁹Si NMR.     

Asymmetric Hydrogenation of α,β‐Unsaturated Nitriles with Base‐Activated Iridium N,P Ligand Complexes

Although many chiral catalysts are known that allow highly enantioselective hydrogenation of a wide range of olefins, no suitable catalysts for the asymmetric hydrogenation of α,β‐unsaturated nitriles have been reported so far. We have found that Ir N,P ligand complexes, which under normal conditions do not show any reactivity towards α,β‐unsaturated nitriles, become highly active catalysts upon addition of N,N‐diisopropylethylamine. The base‐activated catalysts enable conjugate reduction of α,β‐unsaturated nitriles with H₂ at low catalyst loadings, affording the corresponding saturated nitriles with high conversion and excellent enantioselectivity. In contrast, alkenes lacking a conjugated cyano group do not react under these conditions, making it possible to selectively reduce the conjugated C?C bond of an α,β‐unsaturated nitrile, while leaving other types of C?C bonds in the molecule intact.