Synthesis of 3-(4′-Methoxyphenyl)-2,2,4,4-Tetramethylpentane and Some Cyclic Analogs

1986 ◽  
Vol 39 (12) ◽  
pp. 2095 ◽  
Author(s):  
DJ Collins ◽  
HA Jacobs
Keyword(s):  
Methanesulfonic Acid ◽  
Similar Reaction ◽  
Reaction Sequence ◽  
Quinone Methides ◽  
Hydride Reduction ◽  
Lithium Aluminium ◽  
Clemmensen Reduction ◽  
Analogous Manner ◽  
Hydrolysis Of ◽  
Zinc Iodide

Reaction of 1-methoxy-2-methyl-1-trimethylsilyloxyprop-1-ene (8) with 1-acetoxy-1-(4′-methoxyphenyl)-2,2-dimethylpropane (7b) in the presence of zinc iodide gave 84% of methyl 3-(4′methoxyphenyl)-2,2,4,4- tetramethylpentanoate (9a), which was reduced with lithium aluminium hydride to 3-(4′-methoxyphenyl)-2,2,4,4-tetramethylpentan-1-ol(12a). Hydride reduction of the derived tosylate (12b) afforded 3-(4′-methoxyphenyl )-2,2,4,4-tetramethylpentane (5b) which upon demethylation yielded the corresponding phenol (10a). In an analogous manner, 1-acetoxy-1-(4′-methoxyphenyl)-2-methylpropane (7d) was converted into 3- (4′-hydroxyphenyl)-2,2,4-trimethylpentane (10b). By a similar reaction sequence, 6-methoxy-2,2-dimethyl-3,4- dihydronaphthalen-1(2H)-one (14) was transformed into 6-hydroxy-2,2- dimethyl-1-(1′,1′-dimethylethyl)-1,2,3,4-tetrahydronaphthalene (16b). Hydrolysis of the ester (9a) and cyclization of the resulting carboxylic acid (19) by treatment with methanesulfonic acid at 20° for 18 h afforded 3-(1′, 1′-dimethylethyl)-6-methoxy-2,2-dimethyl-2,3-dihydro-1H-inden-1-one (20). Clemmensen reduction of this followed by demethylation yielded 1-(1′,1′-dimethylethyl)-2,2-dimethyl-2,3-dihydro-1H-inden-5-ol (21b). Attempts to oxidize the phenols (10a), (10b), (16b) and (21b) to the corresponding quinone methides by conventional methods failed.

The structure and function of oestrogens. VIII. Synthesis of 5,5, 10b-Trimethyl-cis-4b,5,6,10b,11,12-hexahydrochrysene-2,8-diol from 6-Methoxy-3,4-dihydronaphthalen-1(2H)-one

1984 ◽  
Vol 37 (11) ◽  
pp. 2279 ◽  
Author(s):  
DJ Collins ◽  
JD Cullen ◽  
GD Fallon ◽  
BM Gatehouse
Keyword(s):  
Methanesulfonic Acid ◽  
Enol Ether ◽  
X Ray ◽  
X Ray Crystallography ◽  
Hydride Reduction ◽  
Lithium Aluminium ◽  
Ring Junction ◽  
Clemmensen Reduction ◽  
And Function ◽  
Zinc Iodide

Treatment of 2-hydroxymethylene-6-methoxy-3,4-dihydronaphthalen-1(2H)-one (13a) with p-meth-oxyphenyllead triacetate afforded 93% of 2-formyl-6-methoxy-2-(p-methoxyphenyl)-3,4-dihydro- naphthalen-1(2H)-one (14a) which upon deformylation and methylation gave 60% of 6-methoxy- 2-(p-methoxyphenyl)-2-methyl-3,4-dihydronaphthalen-1(2H)-one (17). An alternative route to the α α'-disubstituted ketone (17) by way of 6-methoxy-2-methyl-3,4-dihydronaphthalen-1(2H)-one (15) and 2-chloro-6-methoxy-2-methyl-3,4-dihydronaphthalen-1(2H)-one (16) was less efficient. Lithium aluminium hydride reduction of the ketone (17) followed by acetylation yielded 80% of 1 ξ acetoxy- 6-methoxy-2-(p-methoxyphenyl)-2-methyl-1,2,3,4-tetrahydronaphthalene (23), treatment of which with the trimethylsilyl enol ether of ethyl 2-methylpropanoate in the presence of zinc iodide afforded 71% of ethyl (1SR,2RS)-2-methyl-2-[6'-methoxy-2'-(p-methoxyphenyl)-2'-methyl-1',2 ',3',4'-tetrahydronaphthalen-yl'ξ-yl]propanoate (26a). Treatment of the ester (26a) or the corresponding acid (26b) with methanesulfonic acid yielded 68 or 82% respectively, of 2*-dimethoxy-5,5,10b-trimethyl- cis-4b,10b,11,12-tetrahydrochrysen-6(5H)-one (27a); Clemmensen reduction of this followed by demethylation with hydrobromicacidin aceticacid gave 49% of cis-5,5,10b-trimethyl-4b,5,6,10b,11,12- hexahydrochrysene-2,8-diol (7a). The sterochemistry of the ring junction in compound (7a) was established by X-ray crystallography of the corresponding dimethyl ether (27b).

The synthesis of methyl 2-O-benzoyl-3,4-O-(S)- and methyl 2-O-benzoyl-3,4-O-(R)-benzylidene-β-L-ribopyranoside

1977 ◽  
Vol 55 (23) ◽  
pp. 4066-4070 ◽  
Author(s):  
David M. Clode
Keyword(s):  
Acid Hydrolysis ◽  
Similar Reaction ◽  
Reaction Sequence ◽  
Hydrolysis Of

Benzylidenation of methyl β-L-arabinopyranoside, by the method of Oldham and Honeyman, followed by benzoylation, gave methyl 2-O-benzoyl-3,4-O-(S)-benzylidene-β-L-arabinopyranoside (1). Selective acid hydrolysis of a 1:1 mixture of the diastereomeric forms of methyl 2-O-benzoyl-3,4-O-benzylidene-β-L-arabinopyranoside gave the (R)-isomer (3). Debenzoylation of 1 and 3 gave methyl 3,4-O-(S)-and methyl 3,4-O-(R)-benzylidene-β-L-arabinopyranoside (2 and 4) respectively. Oxidation of 2, followed by reduction and benzoylation, gave methyl 2-O-benzoyl-3,4-O-(S)-benzylidene-β-L-ribopyranoside (7). A similar reaction sequence with 4 gave methyl 2-O-benzoyl-3,4-O-(R)-benzylidene-β-L-ribopyranoside (8).

Syntheses of N-substituted 3,3,4-triphenyl-4-benzoylazetidin-2-ones and 3′,3′-diphenyl spiro(acenaphthen-1-one-2,4′-azetidin-2′-ones); novel examples exhibiting a high reactivity of imino group in ketoimines

1982 ◽  
Vol 60 (14) ◽  
pp. 1901-1906 ◽  
Author(s):  
S. B. Singh ◽  
K. N. Mehrotra
Keyword(s):  
High Reactivity ◽  
Base Hydrolysis ◽  
Similar Reaction ◽  
Lithium Aluminium Hydride ◽  
Carbonyl Groups ◽  
Imino Group ◽  
Hydride Reduction ◽  
Lithium Aluminium ◽  
Selective Reactivity ◽  
Comparative Reactivity

The reaction of 2-diazo-1,2-diphenylethanone (1) with 2-imino-1,2-diphenylethanones 2a–e gave new N-substituted 3,3,4-triphenyl-4-benzoylazetidin-2-ones 3a–e, together with 1,1′,2,2′-tetraphenyl-2,2′-azinodiethanone (4). Similar reaction of 1 with 2-iminoacenaphthenones 6a, b yielded N-substituted 3′,3′-diphenyl spiro(acenaphthen-1-one-2,4′-azetidin-2′-ones) 7a, b and ketazine 4. Lithium aluminium hydride reduction of azetidinones 3a, b gave 4-α-hydroxybenzylazetidin-2-ones 5a, b. The spiro azetidinones 7a, b on reduction with sodium borohydride yielded spiro(1-hydroxyacenaphthene-2,4′-azetidin-2-ones) 8a, b. The azetidinones 3a–e and 7a, b were found to be unaffected by either acid or base hydrolysis. The marked selective reactivity of the imino group as compared to the carbonyl group towards diphenylketene has been observed in the present studies. The comparative reactivity of carbonyl groups present in azetidinones 3a, b and 7a, b has been presented.

The Structure and Function of Estrogens. IX. Synthesis of the trans Isomer of 5,5,10b-Trimethyl-4b,5,6,10b,11,12-hexahydrochrysene-2,8-diol

1988 ◽  
Vol 41 (5) ◽  
pp. 735 ◽  
Author(s):  
DJ Collins ◽  
JD Cullen
Keyword(s):  
Trans Isomer ◽  
Methanesulfonic Acid ◽  
Structure And Function ◽  
Clemmensen Reduction ◽  
And Function ◽  
Zinc Iodide ◽  
Cis Isomer

Alkylation of ketene methyl trimethylsilyl acetal (10) with 1ξ-acetoxy- 6-methoxy-2-(p- methoxyphenyl )-2-methyl-1,2,3,4-tetrahydronaphthalene (9) in the presence of zinc iodide gave 84% of methyl (1′RS,2′RS)-2- [6′-methoxy-2′-(p-methoxyphenyl )-2?-methyl-1′,2′,3′,4′- tetrahydronaphthalen-1′-yl] ethanoate (11a). Cyclization of the derived acid (11b) with methanesulfonic acid gave 89% of 2,8-dimethoxy-10b-methyl-cis-4b,10b,11,12-tetrahydrochrysen-6(5H)-one (12a), Clemmensen reduction of which afforded 52% of 2,8-dimethoxy-4b-methyl-cis- 4b,5,6,10b,11,12-hexahydrochrysene (12b). Oxidation of (12b) with dichlorodicyanobenzoquinone gave 70% of the conjugated enone (4), which upon hydrogenation over 10% palladium/charcoal gave a 5:1 ratio of 2,8-dimethoxy-10b-methyl-trans-4b,10b,11,12-tetrahydrochrysen-6(5H)-one (14) and the cis isomer (12a). Exhaustive methylation of the trans ketone (14) yielded 49% of 2,8-dimethoxy-5,5,10b-trimethyl-trans-4b,10b,11,12-tetrahydrochrysen-6(5H)-one (16), which upon Clemmensen reduction followed by O- demethylation afforded 5,5,10b-trimethyl-trans-4b,5,6,10b,11,12-hexahydrochrysene-2,8-diol(2).

scholarly journals Pretreatment of Switchgrass for Production of Glucose via Sulfonic Acid-Impregnated Activated Carbon

Processes ◽  
2021 ◽  
Vol 9 (3) ◽  
pp. 504
Author(s):  
Yane Ansanay ◽  
Praveen Kolar ◽  
Ratna Sharma-Shivappa ◽  
Jay Cheng ◽  
Consuelo Arellano
Keyword(s):  
Activated Carbon ◽  
Sulfonic Acid ◽  
Solid Acid ◽  
Methanesulfonic Acid ◽  
Biofuel Production ◽  
Acid Catalysts ◽  
Effects Of Temperature ◽  
Carbon Catalysts ◽  
Hydrolysis Of

In the present research, activated carbon-supported sulfonic acid catalysts were synthesized and tested as pretreatment agents for the conversion of switchgrass into glucose. The catalysts were synthesized by reacting sulfuric acid, methanesulfonic acid, and p-toluenesulfonic acid with activated carbon. The characterization of catalysts suggested an increase in surface acidities, while surface area and pore volumes decreased because of sulfonation. Batch experiments were performed in 125 mL serum bottles to investigate the effects of temperature (30, 60, and 90 °C), reaction time (90 and 120 min) on the yields of glucose. Enzymatic hydrolysis of pretreated switchgrass using Ctec2 yielded up to 57.13% glucose. Durability tests indicated that sulfonic solid-impregnated carbon catalysts were able to maintain activity even after three cycles. From the results obtained, the solid acid catalysts appear to serve as effective pretreatment agents and can potentially reduce the use of conventional liquid acids and bases in biomass-into-biofuel production.

Studies on epoxides. Part II. Abnormal lithium aluminium hydride reduction of cis 3,4-epoxy-5-hydroxycholestanes

1967 ◽  
Vol 8 (52) ◽  
pp. 5261-5263 ◽  
Author(s):  
E. Glotter ◽  
S. Greenfield ◽  
D. Lavie
Keyword(s):  
Lithium Aluminium Hydride ◽  
Hydride Reduction ◽  
Lithium Aluminium

A Synthesis of 2-Amino-2,6-dideoxy-D-(and L-)galaetose (Fucosamine) and 2-Amino-2,6-dideoxy-D-(and L-)talose (Pneumosamine)

1973 ◽  
Vol 51 (6) ◽  
pp. 974-977 ◽  
Author(s):  
Malcolm B. Perry ◽  
Virginia Daoust
Keyword(s):  
Similar Reaction ◽  
Reaction Sequence ◽  
Reaction Conditions ◽  
Nef Reaction ◽  
Methanolic Ammonia

5-Deoxy-D-lyxose underwent base-catalyzed addition with nitromethane to give a mixture of 1,6-dideoxy-1-nitro-D-galactitol and 1,6-dideoxy-1-nitro-D-talitol (ca. 2:1). Acetylation of the crystalline 1,6-dideoxy-1-nitro-D-galactitol gave 2,3,4,5-tetra-O-acetyl-1,6-dideoxy-1-nitro-D-galactitol which on treatment with methanolic ammonia afforded 2-acetamido-1,2,6-trideoxy-1-nitro-D-talitol and 2-acetamido-1,2,6-trideoxy-1-nitro-D-galactitol (ca. 3:1) which under the modified Nef reaction conditions gave 2-acetamido-2,6-dideoxy-D-talose and 2-acetamido-2,6-dideoxy-D-galactose respectively. The glycoses were converted to 2-amino-2,6-dideoxy-D-talose hydrochloride and 2-amino-2,6-dideoxy-D-galactose hydrochloride on hydrolysis with hydrochloric acid.A similar reaction sequence applied to 5-deoxy-L-lyxose afforded the L-enantiomorphic intermediates, and gave 2-amino-2,6-dideoxy-L-talose hydrochloride and 2-amino-2,6-dideoxy-L-galactose hydrochloride as final products.

The synthesis of Cyclododecane-r-1,c-5,c-9-triamine and r-1,c-5,c-9-Tris(2,3-dimethoxybenzamido)cyclododecane

1975 ◽  
Vol 28 (3) ◽  
pp. 673 ◽  
Author(s):  
DJ Collins ◽  
C Lewis ◽  
JM Swan
Keyword(s):  
Aqueous Solution ◽  
Acid Hydrolysis ◽  
Sulphuric Acid ◽  
Sodium Carbonate ◽  
Sodium Azide ◽  
Room Temperature ◽  
Dimethyl Formamide ◽  
Lithium Aluminium Hydride ◽  
Lithium Aluminium ◽  
Hydrolysis Of

Treatment of cyclododecane-r-1,c-5,c-9-triyl tris(p-toluenesulphonate) with sodium azide in dimethyl-formamide at 100� for 6 h gave the corresponding cis,cis-triazide which upon hydrogenation or reduction with lithium aluminium hydride gave cyclododecane-r-1,c-5,c-9-triamine, isolated as the tris-salicylidene derivative. Acid hydrolysis of this, removal of the salicylaldehyde, and treatment of the aqueous solution with sodium carbonate and 2,3-dimethoxybenzoyl chloride gave r-1,c-5,c- 9-tris(2,3-dimethoxybenzamido)cyclododecane. ��� Treatment of (E,E,E)-cyclododeca-1,5,9-triene with an excess of acetonitrile and sulphuric acid at room temperature for three days gave 18% of (E,E)-1-acetamidocyclododeca-4,8-diene; no di- or tri-amides were isolated.

Recent findings in oogenesis of Drosophila melanogaster

Development ◽  
1977 ◽  
Vol 39 (1) ◽  
pp. 45-57
Author(s):  
F. Giorgi ◽  
J. Jacob
Keyword(s):  
Drosophila Melanogaster ◽  
Acid Phosphatase ◽  
Ovarian Development ◽  
Superficial Layer ◽  
Blood Proteins ◽  
Selective Hydrolysis ◽  
Internal Lining ◽  
Hydrolysis Of ◽  
Zinc Iodide ◽  
Yolk Platelet

The role played by the vitellogenic oocytes of Drosophila melanogaster in relation to the elaboration of material taken from the haemolymph is examined by ultrastructural cytochemistry. As revealed by the Gomori procedure, acid phosphatase occurs widely over the forming yolk platelets of the cortical and central ooplasm. A number of Golgi apparatuses in thecortical ooplasm are also positively stained with lead precipitates. With the proceeding of the ovarian development it becomes progressively more difficult to demonstrate cytochemically the enzyme over the yolk platelets. In stage 9–10 chambers the acid phosphatase is restricted to the so-called associated body, while the rest of the yolk platelet appears devoid of lead deposits. By using a osmium zinc iodide (OZ1) complex as a preferential staining method for the Golgi apparatus, it has been shown that, apart from the apparatus itself, a number of OZI deposits occur over the superficial layer of the forming yolk platelets. When mature yolk platelets are formed at later stages, the OZI deposits in the yolk platelets come to be restricted to the cap-like region of the superficial layer which contains the associated body. In vitellogenic oocytes, both the internal lining of the limiting membrane of the forming yolk platelets and the associated body of the mature yolk platelets react positively, to cytochemical methods to demonstrate carbohydrates. The present findings are interpreted as indicating the involvement of lysosomal enzymes in the process of maturation of the yolk material. The suggestion is also made that such an involvement is required to accomplish a selective hydrolysis of those blood proteins which have been taken in by vitellogenic oocytes along with yolk precursors.

Sign in / Sign up

Export Citation Format

Share Document