Reactions of 3-butine-2-methyl-2-ol with isothiocyanates

1986 ◽  
Vol 51 (5) ◽  
pp. 1119-1126 ◽  
Author(s):  
Peter Kutschy ◽  
Milan Dzurilla ◽  
Ladislav Kniežo ◽  
Juraj Bernát ◽  
Ján Imrich ◽  
...  
Keyword(s):  
Carbon Atom ◽  
Sodium Hydride ◽  
Derivatives Of

3-Butine-2-methyl-2-ol reacts with isothiocyanates in the presence of sodium hydride in dimethylformamide to give various products depending on structure of the isothiocyanate residue. Isothiocyanates with the NCS group bound to sp2 carbon atom (phenyl, 4-bromophenyl, and styryl isothiocyanates) give the respective 1,3-oxazolidine derivatives. If the NCS group is bound to an sp3-hybridized carbon atom (ethyl and benzyl isothiocyanates), derivatives of 1,3-oxathiolane are formed. Acyl isothiocyanates (benzoyl and 3-phenylpropenoyl isothiocyanates) give products of substitution of the NCS group, viz. 1-butine-3-methyl-3-yl benzoate and 3-phenylpropenoic anhydride.

Synthesis and Biological Effects of N-(2-Phosphonomethoxyethyl) Derivatives of Deazapurine Bases

1993 ◽  
Vol 58 (6) ◽  
pp. 1419-1429 ◽  
Author(s):  
Hana Dvořáková ◽  
Antonín Holý
Keyword(s):  
Biological Effects ◽  
Sodium Hydride ◽  
Cesium Carbonate ◽  
Cytostatic Effect ◽  
Phosphonic Acids ◽  
Dna Viruses ◽  
Purine Bases ◽  
Heterocyclic Bases ◽  
L 1210 Leukemia ◽  
Derivatives Of

Analogs of antiviral 9-(2-phosphonomethoxyethyl)adenine (PMEA,II), containing modified purine bases 1-deazaadenine (VII, 3-deazapurine (XI), 7-deaza-7-cyanoadenine (XIIIb) and 3-deazaguanine (XXIb) were prepared by alkylation of the heterocyclic bases with bis(2-propyl) 2-chloroethoxymethylphosphonate (V) in dimethylformamide in the presence of sodium hydride or cesium carbonate. The obtained protected derivatives were deblocked with bromotrimethylsilane to give the phosphonic acids. 3-DeazaPMEG (XXIb) is active against DNA viruses and exhibits a marked cytostatic effect against L-1210 leukemia.

scholarly journals Synthesis and crystal structures of two purpurin derivatives: 1,4-dihydroxy-2-propoxyanthraquinone and 2-butoxy-1,4-dihydroxyanthraquinone

2017 ◽  
Vol 73 (11) ◽  
pp. 1687-1691 ◽  
Author(s):  
Eric Bosch ◽  
Emily N. McClain
Keyword(s):  
Carbon Atom ◽  
Hydrogen Bonds ◽  
Sodium Hydride ◽  
Maximum Deviation ◽  
Independent Molecule ◽  
Asymmetric Unit ◽  
Terminal Carbon Atom ◽  
Butyl Group ◽  
Independent Molecules ◽  
Hydroxy Groups

The title compounds were obtained by deprotonation of 1,2,4-trihydroxyanthraquinone (purpurin) using sodium hydride followed by reaction with either 1-bromopropane or 1-bromobutane. 1,4-Dihydroxy-2-propoxyanthraquinone crystallizes as a 1:1 solvate from acetonitrile, C17H14O5·CH3CN. The anthraquinone core of the molecule is essentially planar and both hydroxy groups participate in intramolecular O—H...O (carbonyl) hydrogen bonds. The propyl chain is angled slightly above the plane of the anthraquinone moiety with a maximum deviation of 0.247 (2) Å above the plane for the terminal carbon atom. In contrast, 2-butoxy-1,4-dihydroxyanthraquinone, C18H16O5, crystallizes from nitromethane with two independent molecules in the asymmetric unit. The anthraquinone core of each independent molecule is essentially planar and both hydroxy groups on both molecules participate in intramolecular O—H...O(carbonyl) hydrogen bonds. The butyl chain in one molecule is also angled slightly above the plane of the anthraquinone moiety, with a maximum deviation of 0.833 (5) Å above the plane for the terminal carbon atom. In contrast, the butyl group on the second molecule is twisted out of the plane of the anthraquinone core with a torsion angle of 65.1 (3)°, resulting in a maximum deviation of 1.631 (5) Å above the plane for the terminal carbon atom.

Syntheses of Enantiomeric N-(3-Hydroxy-2-phosphonomethoxypropyl) Derivatives of Purine and Pyrimidine Bases

1993 ◽  
Vol 58 (3) ◽  
pp. 649-674 ◽  
Author(s):  
Antonín Holý
Keyword(s):  
Benzoyl Chloride ◽  
Sodium Hydride ◽  
Cesium Carbonate ◽  
Amino Groups ◽  
Heterocyclic Base ◽  
Pyrimidine Bases ◽  
Derivatives Of ◽  
General Method

Methods of preparation of N-(3-hydroxy-2-phosphonomethoxypropyl) (HPMP) derivatives of (2S)- and (2R)-configuration (compounds I and XXVII, respectively) are described. The general method starts from the corresponding N-(2,3-dihydroxypropyl) derivatives which were converted either into the (R)-enantiomers XIII by reaction of the base with (R)-glycidol butyrate (XII) in the presence of cesium carbonate and subsequent methanolysis, or into the (S)-enantiomers XI by alkylation of the base with (R)-2,2-dimethyl-4-tosyloxymethyl-1,3-dioxolane (V) in the presence of the same reagent. The amino groups on the heterocyclic base in compounds XI and XIII were benzoylated by silylation followed by reaction with benzoyl chloride and the obtained N-benzoates XV and XVII on reaction with trityl chloride afforded the corresponding 3'-O-trityl derivatives XVI and XVIII. These compounds were condensed with bis(2-propyl) p-sulfonyloxymethylphosphonate (XXIII) in dimethylformamide in the presence of sodium hydride to give the fully protected diesters XXIV and XXVIII. These compounds could be selectively acid-hydrolyzed to remove the trityl group only under formation of compounds XXXV, or methanolyzed and then acid-hydrolyzed to remove the trityl and N-benzoyl groups and lead to compounds XXVI and XXX, or treated with bromotrimethylsilane to remove the trityl and 2-propyl group to give phosphonates of the type XXXI. All the three types of compounds were then converted into free phosphonates of the (S)-series (I) and the (R)-series (XXVII). Derivatives of cytosine (Ia, XXVIIa), adenine (Ib, XXVIIb), 2,6-diaminopurine (Ic, XXVIIc) and guanine (Id, XXVIId) were prepared. Condensation of the partially blocked adenine deriavtive XXXV with the tosyl derivative XXIII and subsequent deprotection afforded 9-(S)-(2,3-diphosphonomethoxy propyl)adenine (XLIII). Reaction of the same compound XXXV or its (R)-enantiomer XXXVIII with diethyl phosphonate , followed by deblocking, afforded 3'-O-phosphoryl derivatives (S)-HPMPA (XXXVII) and (R)-HPMPA (XL).

Synthesis of Cyclopropyl Amino Acid Derivatives

1992 ◽  
Vol 45 (2) ◽  
pp. 395 ◽  
Author(s):  
CJ Easton ◽  
EW Tan ◽  
CM Ward
Keyword(s):  
Amino Acid ◽  
Sodium Hydride ◽  
Side Chain ◽  
Amino Acid Derivatives ◽  
Protected Amino Acid ◽  
Derivatives Of

Derivatives of α,β-methanovaline, α,β-methanophenylalanine and β-methyl-αβmethanoalanine have been prepared by regioselective side-chain functionalization of suitably protected amino acid derivatives, followed by cyclization with either sodium hydride or 1,8-diazabicyclo[5.4.O]undec-7-ene. The approach used in this work illustrates a method for the synthesis of cyclopropyl amino acid derivatives which is complementary to existing procedures.

Preparation of 2'(3')-O-phosphonylmethyl derivatives of ribonucleosides

1983 ◽  
Vol 48 (3) ◽  
pp. 778-789 ◽  
Author(s):  
Ivan Rosenberg ◽  
Antonín Holý
Keyword(s):  
Alkali Metal ◽  
Metal Hydride ◽  
Sodium Hydride ◽  
Protecting Groups ◽  
Aqueous Alkali ◽  
Subsequent Hydrolysis ◽  
Derivatives Of ◽  
Alkali Metal Hydride

Reaction of 5'-O-tritylribonucleosides I with dimethyl p-toluenesulfonyloxymethanephosphonate (III) followed by hydrolysis afforded 2'(3')-O-phosphonylmethyluridine (IIa), -cytidine (IIb) and -adenosine (IIc). With 2',5'-di-O-trityluridine (IX), this procedure led to the 3'-isomer of IIa, with 3',5'-di-O-trityluridine (X) to the 2'-isomer. 5'-O-Trityluridine (Ia) and -cytidine (Ib) were converted by reaction with iodomethanephosphonic acid and N,N'-dicyclohexylcarbodiimide into the 2'(3')-O-iodomethanephosphonyl derivatives IVa, b which on reaction with sodium hydride and subsequent hydrolysis gave the compounds IIa and IIb. Reaction of compound I or 5'-O-benzoyluridine (VIII) with chloromethanephosphonyl dichloride (V) and removal of the protecting groups afforded 2'(3')-O-chloromethanephosphonylribonucleosides VI which on reaction with sodium hydride, or better with aqueous alkali, gave 2'(3')-O-phosphonylmethyl derivatives of uridine (IIa), cytidine (IIb), adenosine (IIc) and guanosine (IId). 2',3'-O-Isopropylideneribonucleosides XI reacted with the compound V to give, after hydrolysis, 5'-O-chloromethanephosphonyluridine (XIIa) and cytidine (XIIb). These compounds were not affected by an alkali metal hydride or hydroxide.

THE MERCAPTOLYSIS OF GLUCOSE AND GALACTOSE PENTAACETATES

1951 ◽  
Vol 29 (12) ◽  
pp. 1079-1091 ◽  
Author(s):  
R. U. Lemieux
Keyword(s):  
Carbon Atom ◽  
Zinc Chloride ◽  
Intermediate Formation ◽  
Acetoxy Group ◽  
Carbonium Ion ◽  
Chloride Catalyst ◽  
Derivatives Of

The mercaptolysis of the α-and β-pentaacetyl derivatives of glucopyranose and galactopyranose at 0 °C. with zinc chloride catalyst was studied. The β-pentaacetates were rapidly transformed to the corresponding ethyl tetraacetyl-1-thio-β-D-glycosides in excellent yields; however, the α-anomers were highly resistant to the mercaptolytic conditions. The results are interpreted on the basis of a participation by the C2-acetoxy group in the replacements at the lactol carbon atom of the β-pentaacetates with the intermediate formation of a resonance stabilized cyclic carbonium ion.

Carbon-13 Nuclear Magnetic Resonance Spectra of Some Dendroketose and Other Furanose Derivatives

1975 ◽  
Vol 53 (18) ◽  
pp. 2748-2754 ◽  
Author(s):  
Dolatrai M. Vyas ◽  
Harold C. Jarrell ◽  
Walter A. Szarek
Keyword(s):  
Nuclear Magnetic Resonance ◽  
Magnetic Resonance ◽  
Carbon Atom ◽  
Nuclear Magnetic Resonance Spectra ◽  
Branched Chain ◽  
Derivatives Of ◽  
Anomeric Center ◽  
Magnetic Resonance Spectra ◽  
Nuclear Magnetic

The carbon-13 n.m.r. spectra of derivatives of the branched-chain sugars apiose and dendroketose, and of other furanose sugars, are reported. The study has permitted assignment of the configuration at the branching carbon atom and at the anomeric center in the dendroketose derivatives.

Synthesis of Some 2'-C-Alkyl Derivatives of 9-(2-Phosphonomethoxyethyl)adenine and Related Compounds

1994 ◽  
Vol 59 (9) ◽  
pp. 2069-2094 ◽  
Author(s):  
Hana Dvořáková ◽  
Antonín Holý ◽  
Ivan Rosenberg
Keyword(s):  
Reaction Pathway ◽  
Sodium Hydride ◽  
Amino Group ◽  
Trimethylsilyl Derivative ◽  
Phosphonic Acids ◽  
Alkyl Derivatives ◽  
Hydrolysis Of ◽  
Trifluoromethyl Derivative ◽  
Derivatives Of ◽  
Related Compounds

To study the effect of β-substitution in 2'-alkyl derivatives of 9-(2-phosphonomethoxyethyl)adenine (Ia) on the antiviral activity or group specificity, these derivatives were synthesized. 9-(2-Hydroxyalkyl)adenines VIII were prepared by alkylation of adenine with suitably substituted oxiranes XIII or 2-hydroxyalkyl p-toluenesulfonates IV and VI. After protection of the adenine amino group by benzoylation (compounds IX) or amidine formation (compounds X), the intermediates were alkylated with diisopropyl p-toluenesulfonyloxymethanephosphonate (XI) in the presence of sodium hydride. After deprotection, the obtained phosphonate diesters XII were converted into phosphonic acids I by transsilylation and hydrolysis. This synthetic scheme was used for the preparation of ethyl (Ie), propyl (If), 2-propyl (Ig), 2-methylpropyl (Ih), cyclopropyl (Ii), cyclohexyl (Ij), benzyl (Ik) and phenyl (Il) derivatives. The 2'-trifluoromethyl derivative XXIIa was prepared analogously from 9-(2-hydroxy-3,3,3-trifluoropropyl)adenine (XXa), obtained by alkylation of adenine sodium salt with 2-hydroxy-3,3,3-trifluoropropyl bromide. 2'-Trimethylsilyl derivative XIXa was obtained by alkylation of adenine with 2-diisopropylphosphonomethoxy-3-(4-toluenesulfonyloxy)propyltrimethylsilane (XVII) followed by transsilylation and hydrolysis of diester XVIIIa. 2,6-Diaminopurine derivatives XVIIId and XXIIb were obtained analogously. 9-(3-Phosphonomethoxybutyl)adenine (XXVIII) and 9-(2-methyl-2-phosphonomethoxypropyl)adenine (XXXV) were prepared from the corresponding hydroxy derivatives XXVIb and XXXII, respectively, by the same reaction pathway as derivatives I.

scholarly journals Inhibition of α-l-fucosidase by derivatives of deoxyfuconojirimycin and deoxymannojirimycin

1990 ◽  
Vol 265 (1) ◽  
pp. 277-282 ◽  
Author(s):  
B Winchester ◽  
C Barker ◽  
S Baines ◽  
G S Jacob ◽  
S K Namgoong ◽  
...  
Keyword(s):  
Carbon Atom ◽  
Human Liver ◽  
Potent Inhibitor ◽  
Competitive Inhibitor ◽  
Piperidine Ring ◽  
Structural Requirement ◽  
Ph Dependency ◽  
Structural Analogues ◽  
Hydroxy Groups ◽  
Derivatives Of

Deoxyfuconojirimycin (1,5-dideoxy-1,5-imino-L-fucitol) is a potent, specific and competitive inhibitor (Ki 1 x 10(-8) M) of human liver alpha-L-fucosidase (EC 3.2.1.51). Six structural analogues of this compound were synthesized and tested for their ability to inhibit alpha-L-fucosidase and other human liver glycosidases. It is concluded that the minimum structural requirement for inhibition of alpha-L-fucosidase is the correct configuration of the hydroxy groups at the piperidine ring carbon atoms 2, 3 and 4. Different substituents in either configuration at carbon atom 1 (i.e. 1 alpha- and beta-homofuconojirimycins) and at carbon atom 5 may alter the potency but do not destroy the inhibition of alpha-L-fucosidase. The pH-dependency of the inhibition by these amino sugars suggests very strongly that inhibition results from the formation of an ion-pair between the protonated inhibitor and a carboxylate group in the active site of the enzyme. Deoxymannojirimycin (1,5-dideoxy-1,5-imino-D-mannitol) is also a more potent inhibitor of alpha-L-fucosidase than of alpha-D-mannosidase. This can be explained by viewing deoxymannojirimycin as beta-L-homofuconojirimycin lacking the 5-methyl group. Conversely, beta-L-homo analogues of fuconojirimycin can also be regarded as derivatives of deoxymannojirimycin. This has permitted deductions to be made about the structural requirements of inhibitors of alpha- and beta-D-mannosidases.

Tricyclic psychotropic agents containing two chalcogen atoms in the central ring: Derivatives of 11H-dibenz[b,f]-1,4-oxathiepin

1982 ◽  
Vol 47 (3) ◽  
pp. 967-983 ◽  
Author(s):  
Karel Šindelář ◽  
Jiří Holubek ◽  
Miroslav Ryska ◽  
Antonín Dlabač ◽  
Jiřina Metyšová ◽  
...  
Keyword(s):  
Carbon Dioxide ◽  
Sodium Hydride ◽  
Sulfuryl Chloride ◽  
Side Chains ◽  
Central Ring ◽  
Lithium Compounds ◽  
Psychotropic Agents ◽  
Trifluoromethyl Derivative ◽  
Derivatives Of

Reactions of 2-bromobenzyl bromide and its analogues XVII and XXV with 2-hydroxythiophenol resulted in 11H-dibenz[b,f]-1,4-oxathiepin (Ia) and its 2-chloro (Ib) and 2-trifluoromethyl derivative (IC). Treatment of the lithium compounds derived from Ia and Ib with carbon dioxide and dimethylaminoalkyl chlorides gave compounds IIa, Va and VIab; modification of side chains led to amines IVa, VIIa and VIIIa. 11-(1-Methyl-4-piperidyl) derivatives Xbc were obtained by chlorination of compounds Ibc with sulfuryl chloride or N-chlorosuccinimide and the following treatment with 1-methyl-4-piperidylmagnesium chloride. Compound Ib was transformed by oxidation to the sulfone XX affording by treatment with sodium hydride and tert-aminoalkylchlorides the basic sulfones XXI and XXII. While the nuclearly unsubstituted amines with the aliphatic side chains (IVa and VIIa) have intensive antireserpine activity and are potential antidepressants, the 11-(1-methyl-4-piperidyl) derivatives with a substituent in position 2 of the skeleton (Xbc) are potential neuroleptics; the trifluoromethyl derivative Xc especially has outstanding cataleptic and antiapomorphine efficacy.

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