- Configurational Statistics of Poly(cyclohexene carbonate)
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Conformational characteristics of poly(cyclohexene carbonate) (PCHC) have been investigated via molecular orbital (MO) calculations and NMR experiments on model compounds. The MO energies established through comparison with the NMR experiments were applied to the rotational isomeric state scheme with Bernoulli and Markov stochastic processes to yield configurational properties such as unperturbed characteristic ratio, its temperature coefficient, configurational entropy, tacticity entropy, and coherence number of PCHC chains including various stereosequences. trans-PCHC composed of (R,R)- and/or (S,S)-repeating units prefers a tg+t conformation in the O-CH-CH-O bond sequence of the (R,R)-unit, and its unperturbed characteristic ratio depends considerably on stereoregularity: isotactic, 29, and syndiotactic, 0.83 (in chloroform at 25 °C). cis-PCHC comprising (R,S)- and/or (S,R)-units exclusively adopts either g-g+g+ or g-g-g+ conformation in the O-CH-CH-O bond sequence of the (R,S)-unit partly owing to intramolecular hydrogen bonds, and the dependence of the characteristic ratio of cis-PCHC on stereoregularity would be completely opposite to that of trans-PCHC: isotactic, 0.59, and syndiotactic, 25. In terms of the abovementioned characteristic parameters, properties of PCHCs synthesized so far with stereospecific catalysts are discussed.
- Yoshida, Naofumi,Aoki, Daisuke,Sasanuma, Yuji
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p. 9362 - 9374
(2020/11/13)
-
- Discovery of (3-Benzyl-5-hydroxyphenyl)carbamates as new antitubercular agents with potent in vitro and in vivo efficacy
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A series of 3-amino-5-benzylphenol derivatives were designed and synthesized. Among them, (3-benzyl-5-hydroxyphenyl)carbamates were found to exert good inhibitory activity against M. tuberculosis H37Ra, H37Rv and clinically isolated multidrug-resistant M. tuberculosis strains (MIC = 0.625-6.25 μg/mL). The privileged compounds 3i and 3l showed moderate cytotoxicity against cell line A549. Compound 3l also exhibited potent in vivo inhibitory activity on a mouse infection model via the oral administration. The results demonstrated 3-hydroxyphenylcarbamates as a class of new antitubercular agents with good potential.
- Cheng, Ya-Juan,Liu, Zhi-Yong,Liang, Hua-Ju,Fang, Cui-Ting,Zhang, Niu-Niu,Zhang, Tian-Yu,Yan, Ming
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- Levorotatory meptazinol prodrug as well as preparation method and purpose thereof
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The invention provides a levorotatory meptazinol prodrug as well as a preparation method and a purpose thereof, wherein the levorotatory meptazinol prodrug is a compound as shown in a formula I or a stereoisomer, a geometrical isomer, a tautomer, oxynitride, a hydrate, a solvate, a metabolite or a pharmaceutically acceptable salt of the compound as shown in the formula I. The compound is low in hepatic first pass effect and high in bioavailability; a medicine which uses the compound as an active component can be used for treating a neurodegenerative disease or various kinds of acute and chronic pain, such as a wound, postoperative, obstetrical and cancer pain, hemicrania, neuropathic pain and the like.
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Paragraph 0092; 0094; 0095
(2017/07/19)
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- Preparation method of alicyclic and aromatic-aliphatic chloroformate
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The invention belongs to the technical field of fine chemistry, and in particular relates to a preparation method of alicyclic and aromatic-aliphatic chloroformate. The preparation method is characterized in that alicyclic alcohol chloroformate or aromatic-aliphatic alcohol chloroformate is obtained by taking alicyclic alcohol or aromatic-aliphatic alcohol and bis(trichlormethyl)carbonate as raw materials, taking organic base as a catalyst and reacting in an organic solvent under certain reaction temperature and certain reaction time, wherein molar ratio among the alicyclic alcohol or the aromatic-aliphatic alcohol, the bis(trichlormethyl)carbonate and the organic base is 1 to (0.4 to 1) to (1.2 to 3); experiment time and experiment temperature are different in two stages, in the first stage, the reaction temperature is -10 to 0 DEG C, and the reaction time is 2 to 5 hours; in the second stage, the reaction temperature is 0 to 25 DEG C, and the reaction time is 7 to 13 hours; a mass ratio between the organic solvent and the alicyclic alcohol or the aromatic-aliphatic alcohol is (10 to 25) to 1; residue in a reaction system is effectively treated, and reaction waste is also recycled and utilized. The preparation method disclosed by the invention has the characteristics of stable reaction, high reaction yield and product purity, environment protection of a reaction process, low production cost, less emission of three wastes, simpleness in preparation technology and easiness in industrialization.
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Paragraph 0040-0041
(2017/05/16)
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- DEVICE AND PROCESS FOR CONTINUOUS PHOSGENATION
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A continuous process for generation of phosgene from CO and Cl2 and consumption of the phosgene thus generated in a liquid-phase reaction so as to form organic products P. The process is implemented in two successive reactors R1 and R2, the first reactor R1 being a reactor for catalytic synthesis of phosgene from CO and Cl2 gas, and the second reactor R2 being a piston reactor, the second reactor R2 being equipped with a mechanical axial agitation device.
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Page/Page column
(2013/11/19)
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- Perylen-3-ylmethyl: Fluorescent photoremovable protecting group (FPRPG) for carboxylic acids and alcohols
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Perylen-3-ylmethyl demonstrated as a new fluorescent photoremovable protecting group (FPRPG) for carboxylic acids and alcohols. Carboxylic acids including amino acids were protected as their corresponding esters by coupling with FPRPG, perylen-3-ylmethyl. Photophysical studies of caged esters showed that they all exhibited strong fluorescence properties and their fluorescence quantum yields were in the range of 0.85-0.95. Irradiation of the caged esters using visible light (≥410 nm) in aqueous acetonitrile released the corresponding carboxylic acids in high chemical (94-97%) and quantum (0.072-0.093) yields. The results obtained from the photolysis of the caged ester in different solvents indicated that solvent has influence on the rate of photorelease. Further, we also explored the ability of FPRPG, perylen-3-ylmethyl for the protection of alcohols and phenols.
- Jana, Avijit,Ikbal, Mohammed,Singh, N.D. Pradeep
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scheme or table
p. 1128 - 1136
(2012/02/16)
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- NOVEL VINBLASTINE DERIVATIVES, THEIR PREPARATION, USE AND PHARMACEUTICAL COMPOSITIONS COMPRISING THE SAID DERIVATIVES
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The invention provides vinblastine derivatives represented by the following formula 1 or their physiologically acceptable salts, their preparation, use and pharmaceutical compositions comprising the said derivatives. The said vinblastine derivatives show inhibiting activities against tumor cell lines and can be used as medicaments for treating malignant tumors.
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Page/Page column 43
(2009/12/05)
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- Design, synthesis, structure-selectivity relationship, and effect on human cancer cells of a novel series of histone deacetylase 6-selective inhibitors
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To uncover novel histone deacetylase 6 (HDAC6)-selective inhibitors and to elucidate the structural requirements for their inhibitory activity, we designed and prepared a series of thiolate analogues based on the structure of an HDAC6-selective substrate and evaluated their properties by Western blotting and enzyme assays. Several thiolate analogues were found to be potent and selective HDAC6 inhibitors. Study of the structure-selectivity relationship revealed that the presence of a bulky alkyl group and tert-butylcarbamate group in these compounds is important for HDAC6-selective inhibition. Compounds 16b and 20b, the most selective and active compounds in this series, exerted a synergistic inhibition of cancer cell growth in combination with paclitaxel. They also blocked the growth of estrogen receptor α-positive breast cancer MCF-7 cells that had been treated with estrogen. These findings suggested that HDAC6-selective inhibitors have potential as anticancer agents.
- Itoh, Yukihiro,Suzuki, Takayoshi,Kouketsu, Akiyasu,Suzuki, Nobuaki,Maeda, Satoko,Yoshida, Minoru,Nakagawa, Hidehiko,Miyata, Naoki
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p. 5425 - 5438
(2008/03/14)
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- Second generation fluorous DEAD reagents have expanded scope in the Mitsunobu reaction and retain convenient separation features
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First generation fluorous DEAD reagent bis(perfluorohexylethyl)azo dicarboxylate (C6F13(CH2)2O 2-CN=NCO2(CH2)2C6F13, F-DEAD-1) has been shown to underperform relative to diisopropylazodicarboxylate in difficult Mitsunobu reactions involving hindered alcohols or less acidic pronucleophiles (phenols). Two new second generation fluorous reagents bearing propylene spacers instead of the ethylene spacers show expanded reaction scope while retaining the easy fluorous separation features. Byproducts from "half fluorous" reagent perfluorooctylpropyl tert-butyl azo dicarboxylate (C8F17(CH2)3O 2CN=NCO2tBu, F-DEAD-2) can be removed by fluorous flash chromatography, and byproducts from bis(perfluorohexylpropyl)azo dicarboxylate (C6F13(CH2)3O 2CN=NCO2(CH2)3C6F 13, F-DEAD-3) can be removed by fluorous solid-phase extraction. The new reagents promise to provide general and complementary solutions for separation problems in Mitsunobu reactions without restricting reaction scope.
- Dandapani, Sivaraman,Curran, Dennis P.
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p. 8751 - 8757
(2007/10/03)
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- Novel farnesyl protein transferase inhibitors as antitumor agents
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Disclosed are novel tricyclic compounds represented by the formula (1.0): and a pharmaceutically acceptable salt or solvate thereof. The compounds are useful for inhibiting farnesyl protein transferase. Also disclosed are pharmaceutical compositions comprising compounds of formula 1.0. Also disclosed are methods of treating cancer using the compounds of formula 1.0.
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- Method of treating cancer using FPT inhibitors and antineoplastic agents
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Disclosed is a method of treating cancer in a patient in need of such treatment comprising administering a therapeutically effective amount of an FPT inhibitor and therapeutically effective amounts of one or more antineoplastic agents. Methods of treating non small cell lung cancer, squamous cell cancer of the head and neck, CML, AML, non-Hodgkin's lymphoma and multiple myeloma are disclosed.
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- Preparation of chloroformates using bis(trichloromethyl)carbonate
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The synthesis of eight chloroformates using bis(trichloromethyl) carbonate(BTC) is reported. It has been found that the yields by this BTC method are improved over the earlier phosgene method, and sodium hydroxide is better than pyridine as catalyst for the preparation of phenyl chloroformate.
- Shi, Haibo,Hu, Weixiao,Sun, Yaquan
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p. 708 - 709
(2007/10/03)
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- The discovery of BMS-275183: An orally efficacious novel taxane
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The evolution of 2, a C-4-methylcarbonate analogue of paclitaxel with minimal oral bioavailability and oral efficacy, into its C-3′ -t-butyl-3′-N-t-butyloxycarbonyl analogue (15i), a novel taxane with oral efficacy in preclinical models that is comparable to iv administered paclitaxel, is described.
- Mastalerz, Harold,Cook, Donald,Fairchild, Craig R.,Hansel, Steven,Johnson, Walter,Kadow, John F.,Long, Byron H.,Rose, William C.,Tarrant, James,Wu, Mu-Jen,Xue, May Quifen,Zhang, Guifen,Zoeckler, Mary,Vyas, Dolatrai M.
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p. 4315 - 4323
(2007/10/03)
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- Beta lactam compounds and their use as inhibitors of tryptase
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Compounds of the formulas: are disclosed. These compounds inhibit tryptase as well as other enzyme systems or are selective tryptase inhibitors and are useful as antiinflammatory agents particularly in the treatment of chronic asthma.
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Page column 81
(2010/11/29)
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- Farnesyl protein transferase inhibitors
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Disclosed are compounds of the formula: wherein R8represents a cyclic moiety to which is bound an imodazolylalkyl group; R9represents a carbamate, urea, amide or sulfonamide group; and the remaining substituents are as defined herein. Also disclosed is a method of treating cancer and a method of inhibiting farnesyl protein transferase using the disclosed compounds.
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- Cyclohexyloxycarbonyl based orthogonal solid phase peptide synthesis in Boc chemistry
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Application of N-cyclohexyloxocarbonyl (Choc) protection in Boc chemistry on solid phase provides a new possibility for the preparation of protected peptide fragments. A Choc/OcHex protection scheme allows also the assembly of cyclic lactam peptides linked to the resin through the C- terminus. Choc protection is stable under the 1M TMSOTf-thioanisole/TFA cleavage condition at 0°C, but it is removable by anhydrous HF. We have utilized cyclohexyloxycarbonyl as an orthogonal protecting group for the synthesis of a i) bicyclic epitope peptide of glycoprotein D of HSV 1 on BHA resin and ii) fully protected hexapeptide involved in protein transport on Merrifield resin.
- Mezo, Gabor,Mihala, Nikolett,Koczan, Gyoergy,Hudecz, Ferenc
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p. 6757 - 6766
(2007/10/03)
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- (Aryltelluro)formates as precursors of alkyl radicals: Thermolysis and photolysis of primary and secondary alkyl (aryltelluro)formates
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Alkyl (aryltelluro)formates are effective precursors of oxyacyl, methyl, and primary and secondary alkyl radicals. At room temperature, irradiation of a benzene solution of methyl (aryltelluro)-formates 10-12, 2-methylpropyl (aryltelluro)formates 14 and 15, octyl (phenyltelluro)formate (17), cyclohexyl (aryltelluro)formates 19 and 20, 3β-cholestanyl (aryltelluro)formates 22 and 23, cholesteryl (phenyltelluro)formate (24) and benzyl (phenyltelluro)formate (27) with a 250-W low-pressure mercury lamp leads to the formation of oxyacyl radicals (34), which can be trapped by diphenyl diselenide to give the corresponding alkyl (phenylseleno)formates 13, 16, 18, 21, 24, 26, and 28 with excellent overall conversions. Thermolysis of these telluroformates at 160 °C in the dark leads to the formation of methyl and primary and secondary alkyl aryl tellurides 36-43 in excellent yields. Presumably, these transformations involve oxyacyl radicals, which undergo subsequent decarboxylation at the elevated temperature to afford alkyl radicals, which become involved in further radical chemistry. When 1-(benzylseleno)-5-hexyl (phenyltelluro)formate (44) was thermolysed under these conditions, 2-methylselenane (45) was observed as the sole selenium-containing product, demonstrating the synthetic utility of (aryltelluro)formates as alkyl radical precursors.
- Lucas, Mathew A.,Schiesser, Carl H.
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p. 5754 - 5761
(2007/10/03)
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- Rationally designed 'dipeptoid' analogues of cholecystokinin (CCK): N-terminal structure-affinity relationships of α-methyl-tryptophan derivatives
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The structure-affinity relationships (SAR) between the N-terminii of a series of α-methyl-tryptophanylphenethylamide derivatives and the cholecystokinin (CCK) B receptor are discussed. A series of compounds with the general formula R-X-α-methyl-tryptophanylphenethylamide was prepared, where R is a cycloalkyl, a bicycloalkyl or a tricycloalkyl group and X is a urethane, thiourethane, amide, urea or a sulphinamide linking group. The CCK-B receptor binding affinities of these are discussed. The SAR form part of a systematic program for the rational design of 'dipeptoid' analogues of the neuropeptide CCK. Beginning with 1,1-dimethylpropyl (±)-[1-(1H-indol-3-ylmethyl)-1-methyl-2-oxo-2- [(2-phenylethyl)amino carbamate (IC50 = 4720 nM on CCK-B binding affinity) the N-terminal moiety was systematically changed for groups of varying size, shape and lipophilicity until the optimal N-terminal group was obtained and the favoured linking group chosen, resulting in the compound tricyclo[3.3.1.13,7)]dec-2-yl(R)-[(1H-indol-3-ylmethyl)-1-methyl- 2-oxo-2[(2-phenylethyl)amino]ethyl]carbamate with and IC50 = 32 nM on CCK-B receptor binding affinity.
- Eden,Higginbottom,Hill,Horwell,Hunter,Martin,Pritchard,Rahman,Richardson,Roberts
-
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- SYNTHESES DE CARBONATES ET CARBAMATES BENZYLIQUES ET ALLYLIQUES
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Different methods for the preparation of carbonates and carbamates derived from 1-phenylethyl, 2-cyclohexenyl and 1-methyl-2-propenyl are described.These conmpounds have been synthesized by the reactions of alcohols, phenols or amines with chloroformiates, imidazolocarbonates or corresponding mixed p-nitrophenylcarbonates. It is shown that these reactions can also be used for the introduction of 1-phenylethyloxycarbonyl - (I), 2-cyclohexenyloxycarbonyl - (II) and 1-methyl-2-propenyloxycarbonyl - (III) groups into alcohols, phenols and amines for the protection of hydroxyls and amino-groups.
- Kryczka, Boguslaw
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p. 147 - 158
(2007/10/02)
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- KINETICS AND MECHANISM OF THE PHOSGENATION OF ALIPHATIC ALCOHOLS II. EFFECT OF THE SOLVENT ON THE REACTION RATE
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A quantitative analysis of the effect of the characteristics of the medium on the phosgenation rate of alcohols was made by means of the parameters of the Koppel-Palm equation.An equation is proposed which describes the effect of the solvent on the reaction rate and which takes account of the interdependence of the components of nonspecific and specific solvation.The applicability of the proposed equation to other solvolytic reactions was demonstrated.An equation is obtained which makes it possible to asses the phosgenation rate of alcohols in relation to the properties of the medium and the structure of the alcohol.
- Chimishkyan, A. L.,Orlov, S. I.,Elinevskii, A. V.,Grabarnik, M. S.,Shebeko, S. M.
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- KINETICS AND MECHANISM OF PHOSGENATION OF ALIPHATIC ALCOHOLS
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The kinetics of the reaction of phosgene with various aliphatic alcohols were investigated in heptane and dioxane and without a solvent.The effects of the polarity of the medium the structure of the alcohol, and the activation parameters of the process are consistent with an addition-elimination mechanism.
- Orlov, S. I.,Chimishkyan, A. L.,Grabarnik, M. S.
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p. 1977 - 1981
(2007/10/02)
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- 1-Aziridine carboxylic acid derivatives with immunostimulant activity
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2-Substituted-1-aziridine-carboxylic acid esters exhibiting immuno-stimulant activity and of the formula STR1 wherein X is a carbamoyl or alkoxycarbonyl radical, and R1 is an aliphatic hydrocarbon radical optionally substituted by halogen, alkoxy, amino, carbamoyloxy, cycloalkyl, hydroxyl, an imido or heterocyclic radical, cycloalkyl; or aryl, aralkyl, aryloxyalkyl or arylthioalkyl wherein the aryl moiety is optionally substituted by halogen, alkyl, alkoxy, hydroxyl, amino, nitro, cyano, acyl, carbalkoxy, thioalkyl, alkylsulphonyl, phenyl or trifluoromethyl. Counterparts where X is --CN and R1 is as above, except for ethyl, are also new.
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- Radical-initiated Reduction of Chloroformates to Alkanes by Tri-n-propylsilane. A Method for Removal of Unwanted Hydroxy-Groups from Organic Molecules
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Chloroformates of primary and secondary alcohols, produced by the reaction of the alcohol with phosgene, are reduced to the corresponding alkane in excellent yields by reaction with tri-n-propylsilane in the presence of t-butyl peroxide at 140 deg C.Unusually large amounts of initiator are required tO)2 per mol of RO*CO*Cl>.The results are rationalized in terms of a free-radical reaction scheme.
- Jackson, Richard A.,Malek, Farideh
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p. 1207 - 1211
(2007/10/02)
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- Carbamates
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Carbamate compounds of the formula: in which CO.X.CO is the diacyl radical of a polybasic carboxylic acid, and R1 is an optionally substituted hydrocarbyl radical; more particularly, X is a member of the group consisting of a direct link, C1 to C4 alkylene groups, C2 to C3 alkenylene, o-phenylene and p-phenylene and R1 is a member of the group consisting of C1 to C18 alkyl, phenyl, chlorophenyl, nitrophenyl, cyclohexyl and benzyl. These carbamates are useful as cross-linking agents in natural rubbers or synthetic rubbers based on isoprene or butadiene polymers.
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