- Nucleophilic substitution reactions of unbranched alkyl amines using triazine reagents
-
Since amines are present in many organic, biological, and drug molecules, a strategy of synthesizing desired compounds by nucleophilic substitution reactions of these amines is very attractive. By using triazine reagents, we have found that nucleophilic substitution reactions of unbranched alkyl amines via morpholine derivatives are feasible. This method can be performed under milder reaction conditions than those in previously reported methods.
- Kitamura, Masanori,Kitaoka, Yuki,Fujita, Hikaru,Kunishima, Munetaka
-
-
- Chemoselective Homologation-Deoxygenation Strategy Enabling the Direct Conversion of Carbonyls into (n+1)-Halomethyl-Alkanes
-
The sequential installation of a carbenoid and a hydride into a carbonyl, furnishing halomethyl alkyl derivatives, is reported. Despite the employment of carbenoids as nucleophiles in reactions with carbon-centered electrophiles, sp3-type alkyl halides remain elusive materials for selective one-carbon homologations. Our tactic levers on using carbonyls as starting materials and enables uniformly high yields and chemocontrol. The tactic is flexible and is not limited to carbenoids. Also, diverse carbanion-like species can act as nucleophiles, thus making it of general applicability.
- Citarella, Andrea,Holzer, Wolfgang,Ielo, Laura,Langer, Thierry,Miele, Margherita,Pace, Vittorio,Urban, Ernst,Zehl, Martin
-
supporting information
p. 7629 - 7634
(2020/10/12)
-
- Preparation method of p-phenylbutoxybenzoic acid
-
The invention discloses a preparation method of p-phenylbutoxybenzoic acid. The preparation method comprises the following steps: using tetrahydrofuran as an initial raw material; carrying out a catalytic reaction with benzoyl chloride to prepare 4-chlorobutanol benzoate; carrying out a Friedel-Crafts alkylation reaction and hydrolysis on 4-chlorobutanol benzoate and benzene to obtain 4-phenylbutanol, carrying out a reaction on the 4-phenylbutanol and thionyl chloride to obtain 4-phenylchlorobutane, carrying out an alkylation reaction on the 4-phenylchlorobutane and methyl p-hydroxybenzoate under the action of potassium carbonate to obtain methyl p-phenylbutoxybenzoate. The raw materials used in the invention are cheap and easily available, the process is easy to realize industrialization,and the obtained final product has the advantages of high purity, novel route, short synthesis route, no dangerous process and simple equipment.
- -
-
Paragraph 0049-0050
(2020/07/24)
-
- Preparation method for p-phenylbutoxybenzoic acid
-
The invention provides a preparation method for p-phenylbutoxybenzoic acid, belonging to the field of organic synthesis. According to the invention, palladium-based catalytic coupling is adopted, andthe Grignard reaction and the Friedel-Craft reaction are avoided, thereby avoiding the production of blue-green copper ion wastewater and generation of a large amount of acidic wastewater due to usageof aluminum trichloride; the preparation method of the invention is friendly to environment, simple in synthesis route and high in the yield of each step; and halogeno-benzene is used for replacing more expensive phenylmagnesium bromide and used as a starting material, so the preparation cost of p-phenylbutoxybenzoic acid is lowered. The p-phenylbutoxybenzoic acid obtained in the invention has good crystal form, high purity and good solubility. The data of embodiments of the invention show that the total yield of p-phenylbutoxybenzoic acid prepared in the invention is 60% or above, and the HPLC purity of p-phenylbutoxybenzoic acid is 99.9% or above.
- -
-
-
- Organocatalytic Chlorination of Alcohols by P(III)/P(V) Redox Cycling
-
A catalytic system for the chlorination of alcohols under Appel conditions was developed. Benzotrichloride is used as a cheap and readily available chlorinating agent in combination with trioctylphosphane as the catalyst and phenylsilane as the terminal reductant. The reaction has several advantages over other variants of the Appel reaction, e.g., no additional solvent is required and the phosphane reagent is used only in catalytic amounts. In total, 27 different primary, secondary, and tertiary alkyl chlorides were synthesized in yields up to 95%. Under optimized conditions, it was also possible to convert epoxides and an oxetane to the dichlorinated products.
- Longwitz, Lars,Jopp, Stefan,Werner, Thomas
-
supporting information
p. 7863 - 7870
(2019/06/27)
-
- To a synthesis process of benzene butoxy benzoic acid (by machine translation)
-
The invention discloses a synthesis process of benzene butoxy benzoic acid, comprises the following synthetic steps: chlorobenzene with magnesium format obtained by reaction of Grignard reagent, Grignard reagent with 1 - bromo - 4 - chlorobutane coupling reaction to obtain the 1 - chloro - 4 - phenyl butane, 1 - chloro - 4 - phenyl butane with the hydroxy benzoic acid condensation reaction to get the butoxy benzoic acid, its reaction equation as follows: This synthetic route step is simple, easy to operate, in the course of synthesizing highly toxic intermediate [...] and avoids the generation of a large amount of waste water, thus not only environment friendly, thereby saving the production cost, the process is obtained by the synthesis of high-purity para-butoxy benzoic acid, suitable for large-scale industrial production. (by machine translation)
- -
-
Paragraph 0052; 0079-0081; 0083-0085
(2018/10/19)
-
- Halogenation through Deoxygenation of Alcohols and Aldehydes
-
An efficient reagent system, Ph3P/XCH2CH2X (X = Cl, Br, or I), was very effective for the deoxygenative halogenation (including fluorination) of alcohols (including tertiary alcohols) and aldehydes. The easily available 1,2-dihaloethanes were used as key reagents and halogen sources. The use of (EtO)3P instead of Ph3P could also realize deoxy-halogenation, allowing for a convenient purification process, as the byproduct (EtO)3Pa?O could be removed by aqueous washing. The mild reaction conditions, wide substrate scope, and wide availability of 1,2-dihaloethanes make this protocol attractive for the synthesis of halogenated compounds.
- Chen, Jia,Lin, Jin-Hong,Xiao, Ji-Chang
-
supporting information
p. 3061 - 3064
(2018/05/28)
-
- Synthesis of N-ω-phenylalkyl-4-(p-chlorophenyl)-piperidin-4-ol analogues with potent antiproliferative activity against HCT-116 cells
-
Some opioid analogues, such as morphine and loperamide, were reported to exhibit weak antiproliferative activity against tumor cells. In a study of loperamide analogues, we found that adding an N-ω-phenylalkyl group onto the 4-arylpiperidin-4-ol unit can have important effects on the antiproliferative activity of such compounds against HCT-116 cells. We optimized the distance between the phenyl group and 4-arylpiperidin unit to promote such activity.
- Hatae, Noriyuki,Kujime, Eiko,Yano, Keigo,Kizuka, Mami,Ashida, Rina,Choshi, Tominari,Nishiyama, Takashi,Okada, Chiaki,Iwamura, Tatsunori,Yoshimura, Teruki
-
p. 560 - 568
(2019/07/31)
-
- Catalytic Access to Alkyl Bromides, Chlorides and Iodides via Visible Light-Promoted Decarboxylative Halogenation
-
Herein is reported the catalytic, visible light-promoted, decarboxylative halogenation (bromination, chlorination, and iodination) of aliphatic carboxylic acids. This operationally-simple reaction tolerates a range of functional groups, proceeds at room temperature, and is redox neutral. By employing an iridium photocatalyst in concert with a halogen atom source, the use of stoichiometric metals such as silver, mercury, thallium, and lead can be circumvented. This reaction grants access to valuable synthetic building blocks from the large pool of cheap, readily available carboxylic acids.
- Candish, Lisa,Standley, Eric A.,Gómez-Suárez, Adrián,Mukherjee, Satobhisha,Glorius, Frank
-
supporting information
p. 9971 - 9974
(2016/07/19)
-
- Visible light promoted hydrochlorination of olefin over Pt, Au and Pd supported on zirconia
-
The Pt, Au and Pd catalysts supported on zirconia were prepared by the colloid deposition method. The catalytic activities of the catalysts for the hydrochlorination of 4-phenyl-1-butene were investigated under the irradiation of visible light, taking hyd
- Yang, Xuzhuang,Zhu, Huaiyong,Gao, Guanjun,Han, Chenhui,Wang, Jie,Liu, Jie,Lu, Huailiang,Tong, Min,Liang, Xiaoyuan
-
-
- Rasta resin-triphenylphosphine oxides and their use as recyclable heterogeneous reagent precursors in halogenation reactions
-
Heterogeneous polymer-supported triphenylphosphine oxides based on the rasta resin architecture have been synthesized, and applied as reagent precursors in a wide range of halogenation reactions. The rasta resin-triphenylphosphine oxides were reacted with either oxalyl chloride or oxalyl bromide to form the corresponding halophosphonium salts, and these in turn were reacted with alcohols, aldehydes, aziridines and epoxides to form halogenated products in high yields after simple purification. The polymersupported triphenylphosphine oxides formed as a byproduct during these reactions could be recovered and reused numerous times with no appreciable decrease in reactivity.
- Xia, Xuanshu,Toy, Patrick H.
-
supporting information
p. 1397 - 1405
(2014/07/22)
-
- Cross-coupling of alkyl halides with aryl or alkyl Grignards catalyzed by dinuclear Ni(ii) complexes containing functionalized tripodal amine-pyrazolyl ligands
-
Structurally distinctive dinuclear Ni(ii) complexes with furan or thiophene tethered amine-pyrazolyl tripodal hybrid ligands have been synthesized and crystallographically characterized. All complexes are catalytically active towards cross-coupling of aryl/alkyl Grignard reagents with β-H containing alkyl halides at room temperature in the presence of N,N,N',N'- tetramethylethylenediamine (TMEDA). The catalytic efficacy of the complexes is dependent on the tether substituent at the central amine. Two species, Ni(ii) TMEDA and Mg(ii) TMEDA complexes, have been isolated from the catalytic reaction mixtures under different conditions. Some ligand-stabilized Ni(ii) and Mg(ii) bimetallic species have also been identified in the ESI-MS spectra.
- Xue, Fei,Zhao, Jin,Hor, T. S. Andy
-
p. 5150 - 5158
(2013/04/10)
-
- Copper-catalyzed cross-coupling reaction of organoboron compounds with primary alkyl halides and pseudohalides
-
Non-activated alkyl electrophiles, including alkyl iodides, bromides, tosylates, mesylates, and even chlorides, underwent copper-catalyzed cross-coupling with aryl boron compounds and alkyl 9-BBN reagents (see scheme; 9-BBN=9-borabicyclo[3.3.1]nonane). The reactions proceed with practically useful reactivities and thus complement palladium- and nickel-catalyzed Suzuki-Miyaura coupling reactions of alkyl halides.
- Yang, Chu-Ting,Zhang, Zhen-Qi,Liu, Yu-Chen,Liu, Lei
-
p. 3904 - 3907
(2011/05/15)
-
- Microwave accelerated three-component fluoroalkylations: Expeditious routes to fluoropharmaceuticals and PET ligands
-
One-pot three-component coupling methods have been developed to allow in situ preparation of fluoroalkylated arenes and hydrocarbon chain analogs. The methods, which are accelerated under microwave irradiation gives access to ω-fluorinated alkyl, alkenyl, and alkynyl substituted arenes from readily available precursors. The methods involve late stage introduction of the fluorine and are well suited to application in the synthesis of 18F labeled PET imaging agents.
- Placzek, Michael,Labeaume, Paul,Harris, Luke,Ng, Patrick,Daniels, Mathew,Kallmerten, Amy,Jones, Graham B.
-
scheme or table
p. 332 - 335
(2011/02/26)
-
- Preparation, structure, and reactivity of nonstabilized organoiron compounds. Implications for iron-catalyzed cross coupling reactions
-
A series of unprecedented organoiron complexes of the formal oxidation states -2, 0, +1, +2, and +3 is presented, which are largely devoid of stabilizing ligands and, in part, also electronically unsaturated (14-, 16-, 17- and 18-electron counts). Specifically, it is shown that nucleophiles unable to undergo β-hydride elimination, such as MeLi, PhLi, or PhMgBr, rapidly reduce Fe(3+) to Fe(2+) and then exhaustively alkylate the metal center. The resulting homoleptic organoferrate complexes [(Me4Fe)(MeLi)] [Li(OEt2)]2 (3) and [Ph4Fe][Li(Et 2O)2][Li(1,4-dioxane)] (5) could be characterized by X-ray crystal structure analysis. However, these exceptionally sensitive compounds turned out to be only moderately nucleophilic, transferring their organic ligands to activated electrophiles only, while being unable to alkylate (hetero)aryl halides unless they are very electron deficient. In striking contrast, Grignard reagents bearing alkyl residues amenable to β-hydride elimination reduce FeXn (n = 2, 3) to clusters of the formal composition [Fe(MgX)2]n. The behavior of these intermetallic species can be emulated by structurally well-defined lithium ferrate complexes of the type [Fe(C2H4) 4][Li(tmeda)]2 (8), [Fe(cod)2][Li(dme)] 2 (9), [CpFe(C2H4)2][Li(tmeda)] (7), [CpFe(cod)][Li(dme)] (11), or [Cp*Fe(C2H4) 2][Li(tmeda)] (14). Such electron-rich complexes, which are distinguished by short intermetallic Fe-Li bonds, were shown to react with aryl chlorides and allyl halides; the structures and reactivity patterns of the resulting organoiron compounds provide first insights into the elementary steps of low valent iron-catalyzed cross coupling reactions of aryl, alkyl, allyl, benzyl, and propargyl halides with organomagnesium reagents. However, the acquired data suggest that such C-C bond formations can occur, a priori, along different catalytic cycles shuttling between metal centers of the formal oxidation states Fe(+1)/Fe(+3), Fe(0)/Fe(+2), and Fe(-2)/Fe(0). Since these different manifolds are likely interconnected, an unambiguous decision as to which redox cycle dominates in solution remains difficult, even though iron complexes of the lowest accessible formal oxidation states promote the reactions most effectively.
- Fuerstner, Alois,Martin, Ruben,Krause, Helga,Seidel, Guenter,Goddard, Richard,Lehmann, Christian W.
-
p. 8773 - 8787
(2008/12/23)
-
- Cross-coupling of alkyl halides with aryl Grignard reagents catalyzed by a low-valent iron complex
-
A striking reversal of the usual reactivity pattern of aryl Grignard reagents is observed for reactions in the presence of catalytic amounts of the "bare" ferrate complex [Li(tmeda)]2[Fe(C2H 4)4] (1). Highly reduced iron-magnesium clusters may play a decisive role in the exceptionally facile and chemoselective cross-coupling reaction with alkyl halides (see scheme).
- Martin, Ruben,Fuerstner, Alois
-
p. 3955 - 3957
(2007/10/03)
-
- PROCESS FOR PRODUCING 1-CHLORO-4-ARYLBUTANE
-
There is provided an industrially advantageous process for producing a 1-chloro-4-arylbutane represented by the general formula (2): wherein R represents hydrogen, lower alkyl, or lower alkoxy, characterized by reacting 1-bromo-3-chloropropane with a compound represented by the general formula (1): wherein R is as defined above; and X represents chlorine, bromine, or iodine, in a solvent.
- -
-
-
- Preparation of ternary platinum(II) complexes with N-(ω-phenylalkyl)- 1,2-ethanediamine and 2,2′-dipyridine and the effect of the methylene chain length of the N-(ω-phenylalkyl)-1,2-ethanediamine in the complexes on intermolecular interactions with various arylsulfonates
-
A series of ternary complexes comprised of platinum(II), 2,2′-dipyridine, and N-(ω-phenylalkyl)-1,2-ethanediamine was prepared by varying the number (n) of methylene chain carbons between the phenyl group and one of the amino groups of 1,2-ethanediamine. NMR measurements indicated that intramolecular stacking occurred for n=1 and intermolecular stacking occurred for n=3 for several of the aryl sulfonates.
- Goto, Masafumi,Tanaka, Katsutoshi,Sumimoto, Masamitsu,Mori, Hiromasa,Kurosaki, Hiromasa
-
p. 649 - 653
(2007/10/03)
-
- Pyrrolo[2,3-d] pyrimidines as antiviral agents
-
This invention relates to a novel class of 4,5,6,7-substituted non-nucleoside, non-phosphorylatable pyrrolo[2,3-d]pyrimidines which exhibit both significantly lower levels of cytotoxicity and superior antiviral activity than known nucleoside, non-nucleoside, and non-nucleoside, non-phosphorylatable pyrrolo[2,3-d]pyrimidine derivatives, particularly against human DNA viruses such as cytomegalovirus (HCMV) and herpes simplex virus type 1 (HSV-1). These compounds are represented by the following formula: wherein: R4is —NR1R2or oxo; R5is —CN, or —CSNR1R2, or —CONR1R2; R6is —H, or halo, or —NR1R2; wherein R1and R2are independently —H or an aliphatic group; and R7is of the formula R3—Ar, wherein R3is an aliphatic group and Ar is an unsubstituted aryl or an aryl independently substituted with halo, nitro, amino, or aliphatic groups; provided that when R5is a —CN or —CSNH2, and R6is a —H or —NH2, and Ar is a —C6H5or a phenyl substituted with only one aliphatic group, R3is an aliphatic group other than methyl such that —R3— is not a —CH2—; and pharmaceutically acceptable salts, prodrugs and derivatives thereof.
- -
-
-
- Interpretation of retention indices in gas chromatography for establishing structures of isomeric products of alkylarenes radical chlorination
-
By an example of previously uncharacterized products obtained by alkylarenes radical chlorination was demonstrated that combination of various interpretation methods applied to the retention indices (RI) in the gas chromatography on the standard nonpolar phases (comparison of RI of products and initial compounds, characteristics of succession of the chromatographic elution of the structural isomers with the use of estimation of molecular dynamic parameters, application of the additive schemes to RI calculation, and using of structural analogy CH3?Cl for testing the results obtained) permitted unambiguous identification of the structure even without data of mass spectrometry.
- Zenkevich
-
p. 270 - 280
(2007/10/03)
-
- Photosensitive compound
-
Photosensitive compounds having preferably a functional group such as --SO2 Cl, --SO3 H, --SO3 R, STR1 (R, R', R" being alkyl) on a terminal benzene or naphthalene ring connected via a methylene group and STR2 moiety are improved in sensitivity to light and thermal stability, and thus useful in a photo resist.
- -
-
-
- Ethylamine derivatives and antihypertensives containing the same
-
An ethylamine derivative of formula (I): STR1 wherein A represents a carbon atom or a nitrogen atom; B represents a substituted or unsubstituted aralkyl or aryl group; C represents hydrogen, alkyl, aralkyl, or aryl, each of which may optionally be substituted or C may optionally be bonded to A to form an alkylene bridge which is optionally substituted, Q represents a substituted or unsubstituted aryl group, said group optionally being substituted by hetero atom(s) or substituent(s) optionally containing hetero atom(s); and X represents an alkylene bridge having from 2 to 20 carbon atoms and is optionally substituted with groups which include hetero atoms with the non-hetero atom substituents optionally containing hetero atoms.
- -
-
-
- Structure of ω-Arylalkyl Radicals: A 13C CIDNP Investigation
-
Thermolysis of a series of ω-arylalkanoyl m-chlorobenzoyl (and acetyl) peroxides at ca. 100 deg C in cyclohexanone and in hexachloroacetone was studied by using 13C chemically induced dynamic nuclear polarization.Analysis of the observed 13C polarizations indicate that all the three radicals (β-arylethyl, γ-arylpropyl and δ-arylbutyl) have open-chain structures with no evidence for aryl participation resulting in spirocycloalkylcyclohexadienyl radicals.
- Olah, George A.,Krishnamurthy, V. V.,Singh, Brij P.,Iyer, Pradeep S.
-
p. 955 - 963
(2007/10/02)
-