Primary Alcohol Groups Research Articles

A method for the selective bromination of primary alcohol groups

A method for the selective bromination of primary alcohol groups

A synthetic heparinoid from amylose

Aminated (mainly on C-2; d.s. 0.6) 6- O-tritylamylose was selectively N-(trifluoroacetyl)ated, and the product detritylated; the product was re- N-(trifluoroacetyl)ated, and the primary alcohol group on C-6 was oxidized to the carboxyl group (d.s. 0.2) with nitrogen dioxide. The product was de- N-(trifluoroacetyl)ated, and the non-dialyzable fraction of the modified amylose was sulfated and re- N-sulfated, to give a white powder (11.5% S) which had negligible activity as a blood anticoagulant.

Nitration of 1-(3?, 4?-dimethoxyphenyl)-2-(2?-methoxyphenoxy)-3-hydroxypropanone and 1-(3?,4?-dimethoxyphenyl)-2-(2?-methoxyphenoxy)-1,3-propanediol as model compounds in lignin

1. When the model compounds of lignin: 1-(3′,4′-dimethoxyphenyl)-2-(2″-methoxypheaoxy)-3-hydroxy-propanone (III) and 1-(3′,4′-dimethoxyphenyl)-2-(2″-methoxyphenoxy)-1,3-propanediol (VII) are nitrated with 9 moles of conc. HNO3 in CCl4, at 18–20°, theβ-alkyl-arylether linkage in them is retained. This gives reason to believe that this type of bond in lignin is also resistant to the action of cone. HNO3 in anhydrous media. 2. In the nitration of 1-(3′,4′-dimethoxyphenyl)-2-(2″-methoxypheaoxy)-1,3-propanediol, together with entrance of the nitro group into the ring, there occurs electrophilic substitution of the side chain by the nitro group. 3. A large excess of HNO3, used in the nitration of compounds (III) and (VII), leads to the esterification of both the primary and secondary alcohol groups in these compounds, with the formation of the corresponding nitrates. 4. On the basis of the obtained results it is possible to assume that in the nitration of lignin the primary and secondary alcohol groups present in lignin are also responsible for the formation of the nitroester nitrogen. In this connection, the presence of the benzyl alcohol group in LMR facilitates its fragmentation, while the presence of a keto group, conjugated with the aromatic ring, in contrast, facilitates a stabilization of the lignin molecule during its nitration in anhydrous media.

Fatty acid composition and intramolecular structure of triglycerides from adipose tissue of the red deer and the reindeer

AbstractRowett Research Institute, Bucksburn, Aberdeen, AB2 9SBTriglycerides extracted from perinephric, omental and subcutaneous adipose tissue of six female red deer and of two male and one female reindeer were analysed for the composition and intramolecular disposition of their component fatty acids.In their overall fatty acid composition, the triglycerides of normal and pregnant red deer were similar and resembled those of domesticated ruminants; trans‐unsaturated acids were present and the perinephric triglycerides contained a relatively high proportion of stearic acid compared with triglycerides from other bodily sites. The triglycerides from corresponding adipose tissue of lactating hinds contained much less stearic acid and relatively more myristic, palmitic and palmitoleic acids, suggesting that fatty acids of exogenous origin were not being deposited because they were in demand for milk fat synthesis.The adipose tissue triglycerides of the reindeer were unusual in that they were, apparently, mainly of endogenous origin and showed a notable resemblance to the triglycerides of lambs reared on a virtually lipid‐free diet. This was reflected in a comparatively low content of stearic acid in the perinephric triglycerides, and the absence of trans‐unsaturated acids from all the triglycerides. Analysis of the principal feed (‘reindeer moss’, Cladonia) showed that, compared with normal herbage, it is a very poor source of exogenous fatty acids.Regardless of their fatty acid composition, the intramolecular structure of the triglycerides of the red deer and the reindeer conformed to the general distribution pattern common to most animals. Stearic acid was, for the most part, esterified to the primary alcoholic groups of the glycerol moiety (positions 1 and 3), as was palmitic acid, except when it was present in lower overall proportion than stearic acid. Unsaturated acids and the medium‐chain acid, myristic acid, were mainly esterified to the secondary alcohol group (position 2).

Fluoborates of Mn(Re) ?-cyclopentadienyldicarbonylnitrosyl cations and some of their transformations

1. The fluoborates of Mn(Re) π-cyclopentadienyldicarbonylnitrosyl cations are formed when nitronium tetrafluoborate is reacted with cyclopentadienylmanganesetricarbonyl and cyclopentadienylrheniumtricarbonyl. 2. A new method was proposed for the synthesis of carbomethoxy-substituted derivatives of Mn(Re) π-cyclopentadienylcarbonylnitrosyl. 3. Reduction of one of the carbonyl groups of the Re π-cyclopentadienyldicarbonylnitrosyl fluoborate cation to a primary alcohol group occurs when this cation is reacted with sodium borohydride.

Effect of diet and rumen development on the composition of adipose tissue triglycerides of the calf

1. Samples of subcutaneous (inguinal) and perinephric adipose tissue were obtained, at slaughter, from each of twenty male calves. Three were neonatal animals, three were 3 days old and two were fed on reconstituted milk to appetite until they weighed 100 kg. The other twelve calves were given milk until they reached 50 kg live weight; concentrates were then included in the diet until, at 60 kg live weight, six calves were slaughtered. The remaining six calves were raised to 100 kg on concentrates alone. The weight of the empty reticulo-rumen of each slaughtered calf was recorded.2. The component fatty acids of the adipose tissue triglycerides of the neonatal and 3-day-old calves were very similar; about 80% consisted of oleic acid (18:1) and palmitic acid (16:0) and the remainder comprised stearic acid (18:0), palmitoleic acid (16:1) and myristic acid (14:0), together with very small amounts of other acids which, in the glycerides of the 3-day-old calves, included some evidently of colostral origin. The perinephric glycerides of both these groups of calves were somewhat more unsaturated than were those of subcutaneous adipose tissue.3. The continued consumption of milk by the calves slaughtered at 60 kg live weight was reflected in the presence of enhanced proportions of 14:0, 18:2, 17:0 and 17:1 in the depot triglycerides and, in addition, very small amounts of branched-chain acids andtrans18:1 were detected. A similar fatty acid pattern was observed in the triglycerides of the calves which were given milk only until they were 100 kg live weight. In all these calves only limited growth of the rumen took place.4. By contrast, the calves which were raised on solid feed from 60 kg to 100 kg and in which rumen development had taken place had depot triglycerides whose fatty acid composition resembled that found in adult animals. Increased proportions of stearic acid accompanied by relatively large amounts oftrans18:1 were present, evidently as a result of the assimilation of the products of bacterial modification of dietary fatty acids in the rumen.5. Regardless of the age of the calves and the over-all fatty acid composition of their tissue triglycerides, the intramolecular disposition of the fatty acids was similar in that saturated components were present esterified mainly in positions 1 and 3, and unsaturated acids for the most part in position 2; the only major exception to this distribution pattern was in respect oftrans18:1 which, when present, was preferentially esterified to the primary alcoholic groups of the glycerol moiety as if it were a saturated acid.

Partial synthesis of evonoloside

The synthesis of evonoloside has been effected from cannogenol and L-rhamnose with a yield of 35%. It has been shown that when a primary alcohol group (at C19) and a secondary axial hydroxy group (at C3) are present in the aglycone, to introduce the sugar component at C3 it is desirable first to protect the primary OH group by the partial acetylation of the aglycone.

Composition of adipose tissue triglycerides of neonatal and year-old lambs.

AbstractTriglyccrides were isolated from perinephric (internal) and subcutaneous (external) adipose tissue obtained from neonatal lambs and from lambs which had been fed, until they were a year old, on a semi‐synthetic ration or on a diet of grass cubes. the triglycerides went analysed for their fatty acid composition (including trans unsaturated acids) and for the intramolecular distribution of these acids between the primary and secondary alcoholic groups of the glycerol moiety.Whereas in the year‐old lambs (and in adult sheep previously examined), the triglycerides of internal adipose tissue had a higher content of stearic acid and trans unsaturated acid than those of external tissues, the triglycerides from the perinephric and subcutaneous tissues of the neonatal lambs were very similar in fatty acid composition. Palmitic acid and C18 mono‐unsaturated acid together constituted more than 80% of the total acids. This composition resembles that of the subcutaneous triglycerides of the grown animal and suggests that, at all stages of growth, the triglycerides of external tissues are largely the result of endogenous synthesis.The fatty acids of the adipose tissues of the neonatal animals did not contain any of the acids of exogenous origin, such as those with trans double bonds, which characterise the triglycerides of the growing and mature animals, particularly those of the internal depots. Nevertheless, the intramolecular disposition of the fatty acids in the triglycerides formed in utero was similar to that previously observed in triglycerides from both the internal and external depots of the adult sheep. Saturated acids (palmitic and stearic acids) predominated amongst those esterified in the 1‐and 3‐positions of the glycerol moiety and unsaturated acids (almost entirely oleic acid) were the major components esterified in the 2‐position.While the triglycerides from corresponding body sites in the two groups of year‐old lambs were generally quite similar with respect to their content of palmitic acid, stearic acid and C18 mono‐unsaturated acid, the contribution of trans isomer to the total C18 mono‐unsaturated acid was considerably greater in the tissues (particularly perinephric tissue) of the animals fed on grass cube than in the tissues of those given the semi‐synthetic ration. This difference between the two groups of lambs was associated with a corresponding difference in the proportions of C18 trans unsaturated acid in the lipids of the rumen contents of the animals.

Zur Chemie des Phorbols, VIII

Oxidation of phorbol with one mole of lead tetraacetate yields bisdehydrophorbol, tiglophorbol and small amounts of phorbolacton-semiacetal. By chemical and spectroscopic investigations of bisdehydrophorbol and its derivatives its complete structure 16 is derived based upon the partial structures and structural elements of phorbol (1 - 3) which have been deduced in preceding communications. By consideration of the mechanism of the oxidative scission of the cyclopropanol unit in phorbol the structure 15 of this new tetracyclic diterpene is obtained. 15 has a pentamethyl-tetradecahydro-1H-cyclopropabenzazulene skeleton (tiglian) carrying as functional groups a tertiary hydroxyl group, an α,β-unsaturated tertiary 1.2-ketol group, a primary allyl alcohol group and a α- [hydroxycyclopropyl] -carbinol group. Phorbol is 4.9.12β.13.20-pentahydroxy-tigliadien- (1.6) -on- (3) (15) , bisdehydrophorbol 4.9.12β.20-tetrahydroxy-13.15-seco-tigliatrien- (1.6.15) -dion- (3.13) (16) the conformations of which have been determined. The structure of phorbolacton-semiacetal is determined in the following communication of this series. Based upon the structure of phorbol and additional chemical and spectroscopic evidence the structure of tiglophorbol (17) is also derived. With the data provided the relative configuration and the conformation of six out of the eight asymmetric centers of phorbol is determined.

On the composition of lysolecithin, together with a study of the practicability of the method of catalytic oxidation in phosphatides

α-Lysolecithin was prepared from soya bean lecithin with the aid of snake venom. The presence of a secondary alcoholic group in α-lysolecithin could not be ascertained by Infrared spectra. The NMR spectra of hydrogenated lecithin and α-lysolecithin were consistent with their postulated structures. The method of catalytic oxidation with molecular oxygen in the presence of platinum was applied to α-lysolecithin. The conditions of the catalytic oxidation were studied in a series of model substances. The catalytic oxidation of α-lysolecithin does not lead to acyl migration, ester cleavage or C–C-cleavage. Hydrogenated α-lysolecithin yields a ketone on oxidation under weakly acidic conditions. The oxidation product reacts with 2,4-dinitrophenylhydrazine, but does not react with Schiff's reagent; it is optically inactive. Also under weakly alkaline conditions a ketone was formed on oxidation. A primary alcoholic group should have given rise to an aldehyde or a carboxylic acid. β-Lysolecithin yields an aldehyde when oxidized in a weakly acidic solution. The same is true, when phosphatidylglycerol is oxidized. A semi-micro method using catalytic oxidation is described which serves as a tool for the detection of primary alcoholic groups in phosphatides.

Studies on carbohydrate-metabolising enzymes : Part XVII. The enzymic synthesis of some disaccharides containing α- D-glucosyl residues

By the action of an enzyme preparation from Tetrahymena pyriformis, α- D-glucosyl residues may be transferred from phenyl α- D-glucopyranoside to various carbohydrates. By this means, the following disaccharides have been prepared and characterised: 6- O-α- D-glucopyranosyl- D-galactose and - D-mannose, 4- O-α- D-glucopyranosyl- L-xylose, 1- O-α- D-glucopyranosylribitol, 1- O-α- D-glucopyranosylerythritol, 1- O-α- D-glucopyranosyl- D-mannitol, and a mixture of 1- O- and 6- O-α- D-glucopyranosyl- D-glucitol. These results show the preferential transfer of α- D-glucosyl residues to primary alcohol groups in carbohydrate acceptor substrates.

Microbiological oxidation of long-chain aliphatic compounds. II. Branched-chain alkanes.

In a medium containing glucose, the yeast Torulopsis gropengiesseri converts long-chain methyl-branched alkanes into glycolipids by one or more of three metabolic pathways, namely, (i) alkane → alkan-1-ol → alkanoic acid →ω- and/or ω-1-hydroxyalkanoic acid → glycolipid, (ii) alkane → alkan-1-ol → glycolipid, and (iii) alkane → alkan-1-ol →ω- and/or ω-1-hydroxyalkan-1-ol → glycolipid. Pathways (ii) and (iii) are important for the metabolism of alkan-1-ols whose dehydrogenation to alkanoic acids is inhibited by one or more methyl substituents close to the primary alcohol group. Initial oxidation of 2,2-dimethylhexadecane occurs exclusively at the less hindered terminal position which is the predominant site of the initial oxidation of 2-methyl-hexadecane. Alkanoic acids and alkan-1-ols which have methyl substituents close to the functional group give ω- and ω-1-hydroxy-derivatives; alkanoic acids and alkan-1-ols which have methyl substituents at the ω-1-position give ω-hydroxy-derivatives.

The permanganate oxidation of thymidine

Thymidine was oxidised with potassium permanganate at pH 8.5 at 37° and the products separated by paper chromatography. The following were identified: 5,6-dihydroxy-5,6-dihydrothymidine (‘thymidine glycol’), N-(2-deoxy-D-ribofuranosyl)-N′-pyruvoylurea, N-formylurea, and urea. A component, probably 2-deoxy-D-ribofuranosylurea was detected but it amounted to less than 4% of the reaction products. In addition were present three acidic products probably produced by the oxidation of the primary alcohol group at position 5′. Almost no 2-deoxy-D-ribose was present so it apparently must also have been oxidised to acidic products. 5,6-Dihydroxy-5,6-dihydrothymidine was obtained also by oxidation of thymidine with osmium tetroxide and barium chlorate.

The nitrate groups of lignin

1. The O-nitration of 1-veratryl-1- and -3-propanols has shown their different behavior with respect to the action of concentrated HNO3. The benzyl alcohol group is readily esterified by HNO3 with the formation of a nitrate in which the nitrate group exerts a stabilizing action on the molecule. Under the same conditions, 1-veratryl-3-propanol resinifies, forming a nitrate with a low yield, which can be explained by the degradation of the aromatic ring. 2. The formation of nitrate nitrogen in the nitration of lignin through the esterification of the primary alcohol groups can take place when the linkage connecting these groups is stable under the nitration conditions.

Phenyloctadecanol and surface‐active derivatives

AbstractPhenyloctadecanol from the Friedel‐Crafts reaction, like phenylstearic acid, is a viscous oil and a mixture of several position isomers. Gasliquid chromatography of the acetophenone homologs formed by CrO3 oxidation showed it to be a mixture of 13 position homologs, with substitution of the phenyl group at carbon atoms 5–17. A crystalline 17‐phenyloctadecanol was isolated. Reaction of oily phenyloctadecanol with dioxane‐SO3 sulfated the primary alcohol group to give sodium phenyloctadecyl sulfate CH3 (CH2)xCH (C6H5) (CH2)y CH2OSO3Na, where x + y = 15. Reaction of phenyloctadecanol with 2.4 moles of SO3 gave an impure p‐sulfophenyloctadecyl sulfate, hydrolyzed to sodium p‐sulfophenyloctadecanol CH3(CH2)xCH (p‐Cin6) H4SO3Na) (CH2)yCH2OH, and sulfated again with dioxane‐SO3 to disodium p‐sulfophenyl‐octadecyl sulfate CH3(CH2)xCH(p‐C6H4SO3Na) (CH2)yCH2OSO3Na. Foam, detergency, and other surface‐active properties were compared with those of the p‐sulfo anda‐sulfo derivatives of oily phenylstearic acid.

The fatty acid composition and intramolecular structure of triglycerides derived from different sites in the body of the sheep

AbstractTriglycerides were isolated from a number of different tissues obtained from six adult sheep; the tissues including internal fat depots (perinephric and mesenteric), subcutaneous fat depots (rump and chest) and the subcutaneous region of the metatarsal part of the hind limbs and of the pinnae of the ears. The fatty acid composition of these triglycerides was determined by gas‐liquid chromatography and the intramolecular distribution of the acids was studied using pancreatic lipase to remove selectively the fatty acids esterified to the primary alcoholic groups (1‐ and 3‐positions) of the glycerol molecules. Unsaturated fatty acids of the trans configuration were estimated by infra‐red absorption analysis.In confirmation of earlier, less detailed, studies it was found that the triglycerides of the internal tissues contained a much higher proportion of saturated fatty acids (particularly stearic acid) than did those of the external tissues. In the most exposed tissues (legs, ears) oleic acid accounted for as much as 60‐70% of the total fatty acids present. Trans fatty acid (almost entirely C18 mono‐unsaturated) was, like stearic acid, found in greatest concentration in the internal tissue triglycerides.Regardless of their location in the body all the triglycerides examined showed a similar pattern of intramolecular distribution of their major component acids; saturated acids (palmitic acid and stearic acid) were for the most part esterified in the 1‐ and 3‐positions, and oleic acid was found predominantly esterified in the 2‐position. Trans unsaturated acid, when present, showed a similar degree of preferential esterification in the 1‐ and 3‐positions to that observed for stearic acid.It was tentatively concluded that long‐chain fatty acids absorbed from the intestine influence primarily the composition of the triglycerides of internal adipose tissue.

Kinetics of alcohol and polyether polyol‐isocyanate reactions using metal catalysts

AbstractA study has been conducted of the kinetics of the reaction of ether alcohols, primary and secondary methoxypropanols, with phenyl isocyanate in the presence of metal catalysts. The proximity of the methoxy and methyl groups to the hydroxyls had a significant effect on the reaction rates as did the type and concentration of metal catalysts (lead naphthenate or dibutyltin dilaurate). The reaction rates in toluene solution were found to be faster than in Cellosolve acetate solution. The study of the reaction of poly(oxy‐propylene)glycols with isocyanate showed the existence of two rate constants due to the reactions of the primary and secondary alcohol groups present in the glycols. The mechanism of the metal‐catalyzed reaction between alcohols and isocyanates was investigated by means of IR and NMR spectra. No direct evidence of alcohol‐catalyst complex formation could be obtained by IR spectroscopy. NMR spectra indicated the existence of a 1:1 complex in the system dibutyltin dilaurate‐1‐methoxy‐2‐propanol.

The reactions of coumarin, cinnamyl alcohol, butynediol and propargyl alcohol at an electrode on which nickel is depositing

The reactions at the cathode, during nickel electrodeposition, of coumarin, butynediol, propargyl alcohol and cinnamyl alcohol have been investigated. Melilotic acid is the main reduction product of coumarin: a second product is an approximately equimolar mixture of o-hydroxyphenylpropanol and o-propylphenol. Butynediol at pH 4 is reduced to butane. 1:4.diol with cis.2.butene ca 2%, n-butane 1% and propane 1% At pH 1·5 the products are n-butane ca 60%, cis.2.butene 30% and trans.2.butene 10%. Propargyl alcohol gives 100% propane at pH 1·5 and 20% at pH 3. There is some reduction of cinnamyl alcohol to phenylpropane. The products show that a decrease in pH favours reduction of primary alcoholic groups, compared with reduction of >C < or -C≡C-, and support the view that reduction of alcoholic groups proceeds so long as the molecule remains attached to the nickel surface. It follows that reactions leading to more highly reduced productsare likely to be the more important in inhibiting nickel deposition.It appears that an additive with appropriate reduction kinetics under plating conditions will be a levelling agent, the kinetics being determined by pH, additive concentration and potential. An electroreducible compound may therefore be a leveller for a certain combination of these variables. The behaviour of propargyl alcohol suggests the possibility that in some molecules the advantage of forming only gaseous reduction products may be combined with the other parameters necessary for a levelling agent.

Nitration of alcohols at the nitrogen. Communication 1. Thermal effects of the reaction of O-nitration of alcohols with nitric acid

1. The differential thermal effects of the reaction of O-nitration of methanol, ethylene glycol, metriol, pentaerythritol, meso-erythritol, glycerin, and d-mannitol were measured as a function of the nitric acid concentration. 2. Under normal conditions the concentration limit of the nitrating ability of nitric acid for primary alcohol groups is the same for all the alcohols studied (59–60%). 3. It was hypothesized that nitric acid with a concentration below 80% produces selective O-nitration only of the primary alcohol groups in polyhydric alcohols.

Induction of cellular morphogenesis in Myxococcus xanthus. II. Macromolecular synthesis and mechanism of inducer action.

Sadler, William (University of Minnesota, Minneapolis), and Martin Dworkin. Induction of cellular morphogenesis in Myxococcus xanthus. II. Macromolecular synthesis and mechanism of inducer action. J. Bacteriol. 91:1520-1525. 1966.-Net changes in ribonucleic acid (RNA), deoxyribonucleic acid (DNA), and protein syntheses in cells of Myxococcus xanthus during induced, synchronous conversion to microcysts are described. The net synthesis of all three macromolecules was temporarily halted for a brief period during the initiation of shape change. Synthesis then resumed and leveled off when refractile microcysts began to appear. The conversion was completely sensitive, throughout the process, to low concentrations of chloramphenicol and actinomycin D. The uptake of amino acids and uracil was linear throughout the conversion, suggesting that the plateaus in rates of net synthesis of protein and RNA represented a period of rapid turnover. The most effective inducers of microcyst formation were fully saturated aliphatic compounds containing 2 to 4 carbon atoms and at least one primary or secondary alcohol group. Studies with labeled inducer indicated that the inducer need not be taken up by the cells to be effective, and probably interacts with some peripheral structure of the cell. The possibility that induction involves an alteration of a membrane-DNA complex is discussed.