- Isopropenyl acetate, a remarkable, cheap and acylating agent of amines under solvent- and catalyst-free conditions: A systematic investigation
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Isopropenyl acetate was proved to be an efficient reagent for acetylation of amine in the absence of solvent and catalyst. The corresponding acetamides were obtained in very high yields without any purification.
- Pelagalli, Romina,Chiarotto, Isabella,Feroci, Marta,Vecchio, Stefano
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- HOMOGENEOUS TRANSITION-METAL CATALYSIS. CLEAVAGE OF THE C-N BOND OF TERTIARY AMINES BY ACID ANHYDRIDES IN THE PRESENCE OF TRANSITION METAL IONS
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In the presence of transition metal chlorides, acid anhydrides are highly active in promoting the dealkylation of tertiary amines, and good yields of N,N-dialkylamides are obtained.
- Khai, Bui The,Arcelli, Antonio
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- An atom efficient and solvent-free synthesis of structurally diverse amides using microwaves
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An array of structurally diverse amides was synthesized efficiently by combining (primary and secondary) amines and carboxylic acids in one-pot under solvent-free microwave (MW) conditions. In most cases, no racemization was observed with optically active inputs and chiral amides were obtained in high ee or de.
- Gelens, Edith,Smeets, Luc,Sliedregt, Leo A.J.M.,Van Steen, Bart J.,Kruse, Chris G.,Leurs, Rob,Orru, Romano V.A.
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- A novel and efficient oxidation of 1,2-amino alcohols to dialkylamides
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The oxidation of 1,2-amino alcohols and α-amino ketones can be efficiently performed using potassium hydroxide in the presence of air. This novel procedure affords carboxylic derivatives in excellent yields and high purity.
- García-Valverde, María,Pedrosa, Rafael,Vicente, Martina
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Read Online
- Hydrosilylative reduction of primary amides to primary amines catalyzed by a terminal [Ni-OH] complex
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A terminal [Ni-OH] complex1, supported by triflamide-functionalized NHC ligands, catalyzes the hydrosilylative reduction of a range of primary amides into primary amines in good to excellent yields under base-free conditions with key functional group tolerance. Catalyst1is also effective for the reduction of a variety of tertiary and secondary amides. In contrast to literature reports, the reactivity of1towards amide reduction follows an inverse trend,i.e., 1° amide > 3° amide > 2° amide. The reaction does not follow a usual dehydration pathway.
- Bera, Jitendra K.,Pandey, Pragati
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p. 9204 - 9207
(2021/09/20)
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- Method for promoting acylation of amine or alcohol by carbon dioxide
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The invention relates to a method for promoting acylation of amine or alcohol by carbon dioxide, which comprises the following steps of: mixing an amine compound, carboxylate or thiocarboxylate compound and a reaction solvent under the action of carbon dioxide, and reacting to obtain an amide compound, or under the action of carbon dioxide, mixing the alcohol compound, the thiocarboxylate compound and the reaction solvent [gamma]-valerolactone, and reacting to obtain the ester compound. According to the invention, under the promotion action of carbon dioxide, carboxylate or thiocarboxylate is used as an acylation reagent, and amine and alcohol are converted into amide and ester compounds in the absence of a transition metal catalyst, so that acylation reagents such as acyl chloride or anhydride with irritation and corrosivity are avoided; and the method has the advantages of simple operation, mild reaction conditions, high tolerance of substrate functional groups, strong applicability and high yield, and provides an efficient, reliable and economical preparation method for synthesis of amide and ester compounds.
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Paragraph 0033-0034
(2021/05/29)
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- Adamantylation of N-aryl and N-arylalkyl acetamides in trifluoroacetic acid
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Alkylation of N-aryl and N-arylalkyl acetamides with hydroxy adamantane derivatives in trifluoroacetic acid was studied. The differentiating effect of trifluoroacetic acid on the regio-selectivity of adamantylation of o-alkyl-substituted acetanilides was established, leading to energetically more stable products of para-substitution with respect to the alkyl group (the content of para-alkyl isomers is 93–94percent). This enabled the synthesis of adamantylaminoarenes in 83–99percent yields and with 95–99percent purity.
- Kireeva, A. V.,Nakhod, M. A.,Novakov, I. A.,Orlinson, B. S.,Pichugin, A. M.,Porkhun, V. I.,Potaenkova, E. A.,Savelyev, E. N.,Vostrikova, O. V.,Zavyalov, D. V.
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p. 1096 - 1101
(2020/07/25)
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- Fe3O4@PEG core/shell nanoparticles as magnetic nanocatalyst for acetylation of amines and alcohols using ultrasound irradiations under solvent-free conditions
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Abstract: Ultrasound irradiation was used to prepare one-pot Fe3O4@PEG core/shell nanostructure for the first time. The morphology, structure, and physicochemical properties were specified by different analytical techniques including field emission scanning electron microscopy, Fourier transform infrared spectroscopy, energy-dispersive X-ray spectroscopy, transmission electron microscopy, X-ray powder diffraction, and vibrating sample magnetometer. For acetylation of phenols, alcohols, and amines, the synthesized Fe3O4@PEG core/shell nanoparticles were used as an efficient heterogeneous and green catalyst with acetic anhydride under sonication applying mild reaction conditions. Different electron-withdrawing and electron-donating substrates indicate a prominent yield of desired products with the merit of reusability of Fe3O4@PEG nanocatalyst and magnetic separation. Graphical Abstract: [Figure not available: see fulltext.].
- Veisi, Hojat,Nikseresht, Ahmad,Rostami, Afsaneh,Hemmati, Saba
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p. 507 - 520
(2018/10/24)
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- Preparation of Polydopamine Sulfamic Acid-Functionalized Silica Gel as Heterogeneous and Recyclable Nanocatalyst for Acetylation of Alcohols and Amines Under Solvent-Free Conditions
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To fabricate SiO2/PDA–SO3H nanocatalyst, a suitable method is designed for the loading of sulfonic acid groups on the surface of polydopamine (PDA)-encapsulated SiO2 nanoparticles. To bridge the gap between heterogeneous and homogeneous catalysis, surface functionalization of silica gel is an elegant procedure. The morphology, structure, and physicochemical features were specified using different analytical techniques including field emission scanning electron microscopy (FESEM), Fourier transformed infrared spectroscopy (FT-IR), high resolution-transmission electron microscopy (HR-TEM), energy dispersive X-ray spectroscopy (EDS), wavelength-dispersive X-ray spectroscopy (WDX), X-ray photoelectron spectroscopy (XPS), and back titration. The SiO2/PDA–SO3H nanoparticles are efficient nanocatalysts for the acetylation of many alcohols, phenols, and amines with acetic anhydride under solvent-free conditions in good to excellent yields. Moreover, the reuse and recovery of the catalyst was shown seven times without detectible loss in activity. Graphical Abstract: [Figure not available: see fulltext.]
- Veisi, Hojat,Vafajoo, Saba,Bahrami, Kiumars,Mozafari, Bita
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p. 2734 - 2745
(2018/07/30)
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- Metal-free amidation of carboxylic acids with tertiary amines
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A direct amidation of carboxylic acids with tertiary amines could be carried out in the presence of the Ph3P-I2 activator. With an appropriate reagent addition sequence, a range of carboxylic acids including aliphatic, allylic, and aromatic acids could be converted into their corresponding tertiary amides under mild conditions without requirement of metal catalysis.
- Phakhodee, Wong,Wangngae, Sirilak,Pattarawarapan, Mookda
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p. 60287 - 60290
(2016/07/11)
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- Preparation of conformationally restricted β2,2- and β2,2,3-amino esters and derivatives containing an all-carbon quaternary center
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β-Amino acids are routinely incorporated into peptidic drugs to increase their stability and to incur conformational biases. However, the synthesis of highly substituted β-amino acids still represents a great challenge. A new approach to their preparation is reported involving a Vilsmeier-Haack reaction with nonaromatic carbon nucleophiles. The highly challenging preparation of contiguous tertiary and all-carbon quaternary centers was successfully used to generate several β2,2,3-amino esters, such as derivatives of homoproline, homoalanine, and homopipecolinic esters.
- Romanens, Alexandre,Blanger, Guillaume
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supporting information
p. 322 - 325
(2015/01/30)
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- Catalytic N-Alkylation of Amines Using Carboxylic Acids and Molecular Hydrogen
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A convenient, practical and green N-alkylation of amines has been accomplished by applying readily available carboxylic acids in the presence of molecular hydrogen. Applying an in situ formed ruthenium/triphos complex and an organic acid as cocatalyst, a broad range of alkylated secondary and tertiary amines are obtained in good to excellent yields. This novel method is also successfully applied for the synthesis of unsymmetrically substituted N-methyl/alkyl anilines through a direct three-component coupling reaction of the corresponding amines, carboxylic acids, and CO2 as a C1 source.
- Sorribes, Iván,Cabrero-Antonino, Jose R.,Vicent, Cristian,Junge, Kathrin,Beller, Matthias
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supporting information
p. 13580 - 13587
(2015/11/10)
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- Chemoselective N-deacetylation under mild conditions
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A mild and efficient chemoselective N-deacetylation using the Schwartz reagent at room temperature in rapid time is described. The mild and neutral conditions enable orthogonal N-deacetylation in the presence of some of the common protecting groups (viz. Boc, Fmoc, Cbz, Ts). The deprotection conditions did not induce any epimerization at the chiral amino centre.
- Sultane, Prakash R.,Mete, Trimbak B.,Bhat, Ramakrishna G.
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supporting information
p. 261 - 264
(2014/01/06)
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- Efficient metal-free hydrosilylation of tertiary, secondary and primary amides to amines
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Hydrosilylation of secondary and tertiary amides to amines is described using catalytic amounts of B(C6F5)3. The organic catalyst enables the reduction of amides with cost-efficient, non-toxic and air stable PMHS and TMDS hydrosilanes. The methodology was successfully extended to the more challenging reduction of primary amides.
- Blondiaux, Enguerrand,Cantat, Thibault
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p. 9349 - 9352
(2014/08/05)
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- Synthesis of arylglycines from CO2 through α-amino organomanganese species
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In the presence of three readily available chemicals, Mn powder, BF 3·OEt2, and LiCl, N-acyl-N,O-acetals were successfully converted into the corresponding α-amino acids (arylglycine derivatives) under 1 atm of a CO2 atmosphere in high yields. The LiCl additive is necessary in order to increase the solubility and the nucleophilicity of an organomanganese intermediate. The products thus obtained were transformed into free α-amino acids in two steps.
- Mita, Tsuyoshi,Chen, Jianyang,Sato, Yoshihiro
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supporting information
p. 2200 - 2203
(2014/05/06)
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- Exploitation of a Candida antarctica lipase B-catalysed in situ carboxylic acid activation method for the synthesis of acetanilides
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An efficient biocatalytic method has been developed which provides acetanilides in good yields which are otherwise inaccessible using Candida antarctica lipase B. The process exploits the enzyme-catalysed synthesis of an acyl donor and its in situ reaction with anilines. The method is potentially useful for the synthesis of bulky acetanilides since amide formation occurs through an active site-independent step.
- Lal, Samridhi,Snape, Timothy J.
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- N -acyl DBN tetraphenylborate salts as N -acylating agents
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Air-stable and crystalline N-acyl DBN tetraphenylborate salts have been synthesized from 1,5-diazabicyclo[4.3.0]non-5-ene (DBN) and the corresponding acyl chloride in the presence of sodium tetraphenylborate. The salts have been shown to be effective N-acylating agents, reacting with primary amines, secondary amines, and sulfonamides to form the corresponding N-acylated products in good yields. The DBN hydrotetraphenylborate byproduct can be conveniently removed by filtration, providing pure N-acylated products without the need for further purification. The N-acyl DBN tetraphenylborate salts are attractive alternatives to acyl halides as they can be stored in air without decomposition, avoid the production of free acid during acylation reactions, and can be used under more forcing thermal conditions.
- Taylor, James E.,Jones, Matthew D.,Williams, Jonathan M. J.,Bull, Steven D.
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experimental part
p. 2808 - 2818
(2012/04/23)
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- Poly-(N,N′-dibromo-N-ethyl-benzene-1,3-disulfonamide) and N,N,N′,N′- tetrabromobenzene-1,3-disulfonamide as highly efficient catalysts, and (AC2O/SIO2) as a heterogeneous system for the acetylation of alcohols, amines, and thiols under microwave irradiation
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Chemical Equation Presented Poly-(N,N′-dibromo-N-ethyl-benzene-1,3- disulfonamide) (PBBS) and N,N,N′,N′-tetrabromobenzene-1,3- disulfonamide (TBBDA) are good activators and catalytic reagents for the acetylation of alcohols, amines, and thiols. The presented method has the advantages of mild conditions, chemoselectivity, and good to high yields, and uses noncorrosive, inexpensive, recyclable, and environmentally friendly catalysts. We have also demonstrated that combining SiO2 with microwave energy provides an efficient, fast, convenient, and easy workup procedure for the synthesis of mono- and disubstituted acetates, acetamides, and thioacetamides. Copyright Taylor & Francis Group, LLC.
- Veisi, Hojat,Ghorbani-Vaghei, Ramin,Eskandari, Hosna,Hemmati, Saba,Rezaei, Ardashir,Hajinazari, Somaye,Far, Mohammad Raoof Heidari,Entezari, Azam
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experimental part
p. 213 - 219
(2011/04/24)
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- The role of phase transfer catalysis in the microwave-assisted N-benzylation of amides, imides and N-heterocycles
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The effect of triethylbenzylammonium chloride (TEBAC) was studied on the outcome of the microwaveassisted solid-liquid phase N-alkylation of amides, imides and N-heterocycles using benzyl halides and K2CO3. It was found that while the benzylation of amides may be somewhat promoted by the presence of TEBAC, succinimide and benzimidazole are so reactive that there is no need to use the catalyst. At the same time, the outcome of the benzylation of phenothiazine may be significantly influenced by the presence or absence of TEBAC in respect of N-versus C-alkylation.
- Greiner, Istvan,Sypaseuth, Fanni Daruny,Gruen, Alajos,Karsai, Eva,Keglevich, Gyoergy
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experimental part
p. 529 - 534
(2010/04/23)
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- A convenient and general iron-catalyzed reduction of amides to amines
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While the iron is hot: The first general and efficient iron-catalyzed reduction of secondary and tertiary amides into amines using polymethylhydrosiloxane (PMHS) has been developed (see scheme).
- Zhou, Shaolin,Junge, Kathrin,Addis, Daniele,Das, Shoubhik,Beller, Matthias
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supporting information; experimental part
p. 9507 - 9510
(2010/03/24)
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- Ruthenium(III) acetylacetonate [Ru(acac)3] -An efficient recyclable catalyst for the acetylation of phenols, alcohols, and amines under neat conditions
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A catalytic amount of ruthenium(III) acetylacetonate (2 mol%) [Ru(acac)3] enables solvent-free acetylation of phenols, alcohols, and amines at ambient temperature in good to excellent yields. Furthermore, the catalyst could be recovered and reused at least three times without a significant loss in yields.
- Varala, Ravi,Nasreen, Aayesha,Adapa, Srinivas R.
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p. 148 - 152
(2008/02/11)
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- The application of N,N′dibromo-N,N′-1,2-ethanediyl bis(P-toluenesulfonamide) as a powerful reagent for conversion of carboxylic acids into esters and amides with triphenylphosphine
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In the presence of equivalent amounts of triphenylphenylphosphine and N,N′-dibromo-N,N′-1,2-ethanediylbis(p-toluenesulphonamide) ester and amide compounds can be generated in high yields from the corresponding carboxylic acid and alcohols or amines.
- Khazaei, Ardeshir,Mallakpour, Shadpour,Zolfigol, Mohammad Ali,Ghorbani-Vaghei, Ramin,Kolvari, Eskandar
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p. 1715 - 1721
(2007/10/03)
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- Aluminium dodecatungstophosphate (AlPW12O40) as a highly efficient catalyst for the selective acetylation of -OH, -SH and -NH2 functional groups in the absence of solvent at room temperature
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AlPW12O40 was found to be an effective catalyst for the selective acetylation of alcohols, thiols, and amines in the absence of solvent at room temperature.
- Firouzabadi, Habib,Iranpoor, Nasser,Nowrouzi, Farhad,Amani, Kamal
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p. 764 - 765
(2007/10/03)
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- Z-selective synthesis of α,β-unsaturated amides with triphenylsilylacetamides
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With the purpose of developing a method of preparing Z-α,β-unsaturated amides, the Peterson reaction of the (triphenylsilyl)acetamide Ph3SiCH2COX (1, X = NBn2; 3, X = NMe2) with various aldehydes was examined. The reaction of aromatic aldehydes gave selectivities up to >97:3. It was found that the selectivity was a function of the electronic nature of the aromatic ring and higher Z selectivity was attained with electron-rich aldehydes. With aliphatic aldehydes selectivities up to 92:8 were achieved, and unlike with analogous phosphorus reagents, less sterically hindered aldehydes gave higher Z selectivity. Also, 3, which has a smaller amide group than 1, tended to give rise to higher selectivity. A comparison with the reaction of trimethylsilyl analogues revealed the significance of the phenyl substituents on the silyl group.
- Kojima, Satoshi,Inai, Hiroki,Hidaka, Tsugihiko,Fukuzaki, Tomohide,Ohkata, Katsuo
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p. 4093 - 4099
(2007/10/03)
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- Highly Z-selective synthesis of α,β-unsaturated amides with the Peterson reaction between α-silylamides and aldehydes
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The Peterson reaction of triphenylsilylacetamide Ph3SiCH2CONBn2 with aromatic aldehydes and certain aliphatic aldehydes proceeded to give the corresponding α,β-unsaturated amide with high Z selectivity (up to Z:E = >97:3).
- Kojima,Inai,Hidaka,Ohkata
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p. 1795 - 1796
(2007/10/03)
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- Rare earth exchanged HY zeolite, an efficient catalyst for the synthesis of N-monosubstituted amides
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The use of rare earth exchanged HY (RE HY) zeolite catalyst for the synthesis of N-monosubstituted amides 3a-g starting from alcohols 1 and nitriles 2 in good yields is described
- Deshmukh, A. R. A. S.,Gumaste, V. K.,Bhawal, B. M.
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p. 369 - 371
(2007/10/03)
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- PHELLODENDRINE ANALOGS AND ALLERGY TYPE IV SUPPRESSOR CONTAINING THE SAME AS ACTIVE INGREDIENT
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Phellodendrine analogs represented by general formula (I), wherein A represents the group (a); B represents hydrogen, lower alkyl or lower acyl, or alternatively A and B together with the adjacent nitrogen atom form a substituted 1,2,3,4-tetrahydroisoquinoline ring represented by general formula (II), R11, R12, R21, R22, R31 and R32 represent each hydrogen, hydroxyl or lower alkoxy; n1 represents a number of 0 to 2; n2 represents a number of 1 and 2; and m1 represents a number of 0 to 1, provided tsat when A represents the group (b), and n2 is 2, B is lower acyl, and that when A and B together form a substituted 1,2,3,4-tetrahydroisoquinoline ring, n1 is 1 and m1 is not 0. These analogs (I) and related compounds have an excellent activity of suppressing allergy type IV and hence are utilizable as a medicine efficacious against diseases wherein allergy type IV participates, such as chronic hepatitis, intractable asthma, nephrotic syndrome or rheumatism.
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- Synthesis in dry media coupled with microwave irradiation: Application to the preparation of enaminoketones
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β-diketones react with a variety of amines and aminoesters over clay K10 or silica under microwave irradiation in open vessels to give within a few minutes, the corresponding enaminoketones with good yields. According to the reaction conditions acylamines may also result.
- Rechsteiner,Texier-Boullet,Hamelin
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p. 5071 - 5074
(2007/10/02)
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