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Showing papers on "Ether published in 1974"


Journal ArticleDOI
TL;DR: In this article, a structural scheme for beech lignin was proposed, in which the C9 structural units are linked together by no less then ten different kinds of bonds.
Abstract: The high molecular weight material lignin consists of phenylpropane units linked together by a variety of bond types. During the past eight years, two newly developed degradation procedures have permitted the first direct determinations of the nature of these bonds. The first procedure affords a very mild partial hydrolysis of benzyl ether bonds. Eleven dimeric, trimeric, and tetrameric degradation products were obtained in this way from spruce and beech lignin: they exhibited three different kinds of bonds between the C9 structural units, and their structures have all been elucidated. In the second procedure, the most important kind of bond in lignin, i. e. the arylglycerol-β-aryl ether bond, can be subjected to directed cleavage under mild conditions after introduction of a suitable neighboring group. On application to beech lignin, 91 % of the material was degraded giving monomeric to tetrameric phenols. Complete structural elucidation of the twenty dimeric phenols isolated and a knowledge of their relative yields and the yields of the other fractions obtained by gel filtration permitted a structural scheme to be set up for beech lignin in which the C9 structural units are linked together by no less then ten different kinds of bonds. The structural scheme, which can be readily explained biogenetically, has the same elemental composition as natural beech lignin. Further support for the structural scheme comes from a comparison of the 13C-NMR spectrum of natural beech lignin and a 13C-NMR spectrum calculated for the proposed structure on the basis of about fifty lignin model substances.

336 citations



Patent
23 Sep 1974
TL;DR: In this article, a process for the production of aromatics-rich gasoline boiling-range hydrocarbons from the lower alcohols methanol, ethanol and propanol, or their ethers is described.
Abstract: This specification discloses a process for the production of aromatics-rich gasoline boiling-range hydrocarbons from the lower alcohols methanol, ethanol and propanol, or their ethers. The process is carried out in two or more stages. In the first stage, an alcohol or an ether is contacted with a condensation catalyst to produce a reaction product containing aliphatic dehydration products thereof and water. In a subsequent stage, at least a portion of the product of the first reaction stage is contacted with, as a catalyst, a crystalline aluminosilicate zeolite having a silica to alumina ratio of at least 12 and a constraint index of 1 to 12 to convert it in high yield to gasoline boiling-range hydrocarbons containing a high proportion of aromatics. In a preferred aspect a lower alcohol, suitably methanol, is dehydrated to an ether or a lower olefin or mixtures thereof, in the first stage, and this first stage product is then converted, over the referred to catalyst, to gasoline boiling-range hydrocarbons.

126 citations


Journal ArticleDOI
TL;DR: In this article, a review of the Ullmann condensation as the most important method for the synthesis of aromatic ethers is presented, and the available information about the dependence of reactivity of the reactants on structure and the reaction mechanism is examined and the experimental condensation conditions are discussed.
Abstract: The review deals with the Ullmann condensation as the most important method for the synthesis of aromatic ethers. The available information about the dependence of the reactivity of the reactants on structure and the reaction mechanism is examined and the experimental condensation conditions are discussed. The bibliography includes 241 references.

96 citations


Patent
25 Mar 1974
TL;DR: In this paper, a method of treating a subterranean formation surrounding a well was proposed, where a solvent including a C4 to C10 alkyl ether of polyglycol ether containing from 10 to 22 carbon atoms per molecule was injected into the formation.
Abstract: A method of treating a subterranean formation surrounding a well wherein a solvent including a C4 to C10 alkyl ether of polyglycol ether containing from 10 to 22 carbon atoms per molecule is injected into the formation. The solvent improves permeability to the formation adjacent the wellbore. The solvent may be used as a preflush or afterflush for, or in combination with, other treating agents; or it may be used as the sole essential treating agent.

92 citations


Journal ArticleDOI
TL;DR: A survey of experimentally established conformations of saturated compounds containing the isolated ether group is given in this article, focusing on simple molecules, polymers, and medium and large rings.

87 citations


Journal ArticleDOI
TL;DR: O-Nitrobenzyl ether linkage of the dinucleotides was removed by UV irradiation with wavelength longer than 320 nm and Deprotected UpU and UpA thus obtained were characterized by RNase A digestion.
Abstract: o-Nitrobenzyl group was introduced to the 2'-hydroxyl function of uridine via 2',3'-O-(dibutylstannylene) uridine. The benzylated uridine was protected at the 5'-hydroxyl group with monomethoxytrityl chloride and condensed with 2',3'-O-dibenzoyluridine 5'-phosphate or N,N',2',3'-O-tetrabenzoyladenosine 5'-phosphate using dicyclohexylcarbodiimide (DCC). o-Nitrobenzyl ether linkage of the dinucleotides was removed by UV irradiation with wavelength longer than 320 nm. Deprotected UpU and UpA thus obtained were characterized by RNase A digestion.

79 citations


Journal ArticleDOI
01 Jul 1974-Fuel
TL;DR: In this article, a vitrinite concentrate of Balmer 10, medium-volatile bituminous coal (433), and highvolatile Moss 3 coal (535) were oxidized in air at 85°C for four days to partially destroy the swelling characteristics as measured by the Ruhr dilatometer.

74 citations



Journal ArticleDOI
TL;DR: In this article, the 13C n.m. spectra of the crystalline α-linked disaccharides of benzyl α-D-galactopyranoside were compared with those of the corresponding β-linked isomers.
Abstract: The four tri-O-benzyl ethers of benzyl α-D-galactopyranoside were prepared from benzyl 6-O-allyl-α-D-galactopyranoside. The stability of 4,6-O-propylidene derivatives of benzyl-α-D-galactopyranoside in acidic hydroxylic solvents was noted in this work. The condensations of 2,3,4,6-tetra-O-benzyl-α-D-glucopyranosyl chloride with methanol, benzyl 2,3,4-tri-O-benzyl-α-D-galactopyranoside, and benzyl 3,4,6-tri-O-benzyl-α-D-galactopyranoside in dichloromethane containing triethylamine and tetraethylammonium chloride gave glycosides containing predominantly α-linkages. The 13C n.m.r. spectra of the crystalline α-linked disaccharides, benzyl 6-O-(2,3,4,6-tetra-O-benzyl-α-D-glucopyranosyl)-2,3,4-tri-O-benzyl-α-D-galactopyranoside and benzyl 2-O-(2,3,4,6-tetra-O-benzyl-α-D-glucopyranosyl)-3,4,6-tri-O-benzyl-α-D-galactopyranoside were compared with those of the corresponding β-linked isomers. Treatment of 2,3,4,6-tetra-O-benzyl-D-glucose dimethyl acetal with an acid catalyst in ether gave predominantly methyl 2,3,4,6-tetra-O-benzyl-α-D-glucopyranoside. 3,4,6-Tri-O-benzyl-2-dibenzylamino-2-deoxy-D-glucopyranose was prepared from allyl 2-benzamido-2-deoxy-β-D-glucopyranoside, as a potential intermediate for α-glycoside synthesis in the amino-sugar series.

65 citations


Journal ArticleDOI
TL;DR: In this article, the chemical structure and cure characteristics of a group of phenolic resole resins were studied by means of three major analytical techniques: Gel permeation chromatography, NMR and differential scanning calorimetry.
Abstract: The chemical structure and cure characteristics of a group of phenolic resole resins were studied by means of three major analytical techniques. In particular, the effects on structure and reactivity of formaldehyde/phenol ratio and the type of reaction catalyst used were studied. Gel permeation chromatography was used to determine resin molecular weight distributions, and NMR, to determine chemical structural features. In this connection a selective oxidation procedure, converting free methylol groups to adehydes, has allowed unambiguous determination of methylene ether bridge structures to be made from the NMR data. The F/P ratio in a resole largely determines the type of molecular structures which are formed. However, triethylamine as a catalysts tends to favor methylene ether bridge formation, whereas sodium hydroxide favors methylene bridges. The rate and direction of subsequent thermal cure of the resoles prepared is shown by differential scanning calorimetry to depend markedly on the type of catalyst present during the curing stage. The DSC curing curves are interpreted in the light of the structural information provided by NMR.

Journal ArticleDOI
TL;DR: In this article, the isomerisations of allyl, 2-methylallyl, and but-2-enyl groups by tristriphenylphosphinerhodium(I) chloride are compared with the reactions of these groups with potassium t-butoxide in dimethyl sulphoxide.
Abstract: The isomerisations of allyl, 2-methylallyl, and but-2-enyl groups by tristriphenylphosphinerhodium(I) chloride are compared with the reactions of these groups with potassium t-butoxide in dimethyl sulphoxide.

Journal ArticleDOI
TL;DR: This paper aims to provide a history of insect behaviour in the laboratory and some of the techniques used, as well as some new approaches, that have been developed since the publication of “Chemicals Controlling Insect Behaviour,” Beroza (1970).
Abstract: Renwick, .J. A . A , , Contrib. BoJce Thompsonlnst. 24,337 (1970). Renwick. J. A. A., Viti., J . P., Contrib. Boyce Thompson Inst. 23, 65 (1968). Renwick, J. A. A , , Viti., J . P., Contrib. Boyce Thompnon Inst. 24, 283 ( 1970). Silverstein, R. M. , in “Chemicals Controlling Insect Behaviour,” Beroza. M.. Ed., Academic Press, New York. N. Y., 1970, pp 21-40. Silverstein, R. M.. Brownlee, R. G., Bellas, T. E., b’ood. D. L.. Received for review September 10. 1973. Accepted .January 9. Brown, I,. E., Scicvzce 159,889 (1968). Viti., .J. P., Pitman, G. B.. Nature (London) 218,169 (1969a). Viti., J . P., Pitman, G. B., Can. Entomol. 101,113 (1969b). Viti., .J. P., Renwick, J. A . A,, Contrib. R o ~ c e Thompson Inst. 21,

Patent
30 Oct 1974
TL;DR: Stabilized polyphenylene ether type resin composition obtained by compounding a poly phenylene ether-type resin with one or more of stabilizer-component such as those respectively (a) a high molecular phosphorous ester having at least three phosphorus ester-bondings per molecule, (b) an intermediate product consisting of steric hindered phenols and dicarboxylic acid dihydrazide substitution product; and, if desired, boron oxide as mentioned in this paper.
Abstract: Stabilized polyphenylene ether type resin composition obtained by compounding a polyphenylene ether type resin with one or more of stabilizer-component such as those respectively (a) a high molecular phosphorous ester having at least three phosphorous ester-bondings per molecule, (b) a high molecular phosphorous ester as said above and dicarboxylic acid dihydrazide substitution product, (c) a high molecular phosphorous ester as said above and steric hindered phenols and (d) a high molecular phosphorous ester as said above, steric hindered phenols and dicarboxylic acid dihydrazide substitution product; and, if desired, boron oxide.


Patent
26 Feb 1974
TL;DR: In this paper, a foamable composition consisting of water, calcined gypsum or hydraulic cement and, as a foaming agent, the sodium salt of an Alpha-olefin sulfonate of an olefin having 14 to 20 carbon atoms in the molecule, or the sulfuric acid ester of an alkyl polyglycol ether, which ether is prepared by hydroxyethylation of one mole of a fatty alcohol having a carbon chain of 10 to 14 carbon atoms with, on the average, 3 moles of ethylene oxide, or a mixture
Abstract: This invention relates to a foamable composition comprising water, calcined gypsum or hydraulic cement and, as a foaming agent, the sodium salt of an Alpha -olefin sulfonate of an olefin having 14 to 20 carbon atoms in the molecule, or the sodium salt of the sulfuric acid ester of an alkyl polyglycol ether, which ether is prepared by hydroxyethylation of one mole of a fatty alcohol having a carbon chain of 10 to 14 carbon atoms with, on the average, 3 moles of ethylene oxide, or a mixture of both of the said sodium salts.

Patent
06 Dec 1974
TL;DR: Aromatic bis(ether anhydride)s can be made by a nitro displacement of an N-substituted nitrophthalimide with an alkali diphenoxide to produce an intermediate aromatic bis (etherphthalimide).
Abstract: Aromatic bis(ether anhydride)s can be made by a nitro displacement of an N-substituted nitrophthalimide with an alkali diphenoxide to produce an intermediate aromatic bis(etherphthalimide). Hydrolysis of the aromatic bis(etherphthalimide) to the corresponding tetra-acid salt followed by acidification and dehydration, results in the production of the aromatic bis(ether anhydride). These anhydrides can be used as intermediates for making polyimides. The intermediate aromatic bis(etherphthalimide) can be employed as a plasticizer in polyimide resins.

Patent
25 Jan 1974
TL;DR: In this article, a method of producing butene-1 resides in dimerizing ethylene in the presence of a complex organometallic catalyst of the formula (RO)3 TiR'.
Abstract: The present invention relates to a method of producing butene-1. According to the invention, the method of producing butene-1 resides in dimerizing ethylene in the presence of a complex organometallic catalyst of the formula (RO)3 TiR' .AlR2 "OR + AlR2 "R', where R is an alkyl radical with from 2 to 4 carbon atoms, R' = R or H, R" is the same as R, or a catalyst having the formula Ti(OR)4 + AlR2 "R' and modifiers such as (C5 H5)2 TiCl2, oxygen, metaphenylenediamine or N-phenyl-β-naphthylamine, in the medium of solvents such as n-heptane, n-decane, toluene, diethyl ether, ethyl chloride, vinylbutyl ether, tetrahydrofuran, diphenyl ether, methylphenyl ether and mixtures thereof. The invention will find application in petrochemical processing.

Journal ArticleDOI
TL;DR: In this paper, the thermal decomposition of t-butylmethyl ether has been studied using the VLPP technique using the recommended Arrhenius parameters for the molecular elimination, reaction (1), are A(800°K) = 101 3, 9 sec−1 and Ea (800°k) = 59.0 ± 1.0 kcal/mole.
Abstract: The thermal decomposition of t-butylmethyl ether has been studied using the VLPP technique. The recommended Arrhenius parameters for the molecular elimination, reaction (1), are A(800°K) = 101 3, 9 sec−1 and Ea (800°K) = 59.0 ± 1.0 kcal/mole. No radical reactions occur under the conditions used. These parameters are in good agreement with earlier experimental work and with theoretical estimates of both A and E.

Journal ArticleDOI
TL;DR: In this paper, a new, efficient synthesis of coenzyme Q was described, in which the bromination of 2,3-dimethoxy-5-methyl-p-benzoquinone gives 6-bromo-2,3dimethyl-π-allylnickel bromide, which is then converted to the corresponding hydroquinone diacetate by the action of zinc dust in acetic anhydride.
Abstract: A new, efficient synthesis of coenzyme Q is described. The bromination of 2,3-dimethoxy-5-methyl-p-benzoquinone gives 6-bromo-2,3-dimethoxy-5-methyl-p-benzoquinone, which is then converted to the corresponding hydroquinone diacetate by the action of zinc dust in acetic anhydride. 6-Bromo-2,3-dimethoxy-5-methylhydroquinone diacetate is reacted with 1,1-dimethyl-π-allylnickel bromide in hexamethylphosphoramide at 60 °C to afford a 70% yield of 2,3-dimethoxy-5-methyl-6-prenylhydroquinone diacetate, which is hydrogenolyzed with lithium aluminum hydride in ether and then oxidized with aqueous ferric chloride to give coenzyme Q1 in 76% yield. Similarly, coenzyme Q2, Q9, and Q10, and 6′, 10′, 14′-hexahydrocoenzyme Q4 are synthesized by the reaction of the aryl bromide with π-geranyl-, π-solanesyl-, π-decaprenyl-, and π-phytylnickel bromide respectively and by subsequent treatment with LiAlH4 and FeCl3. The stereochemistry of the products is also described.

Patent
02 Aug 1974
TL;DR: Aromatic bis(ether anhydride)s are prepared from the hydrolysis of the reaction product of a nitro-substituted phenyl dinitrile with a metal salt of a dihydroxy aryl compound in the presence of a dipolar aprotic solvent.
Abstract: Aromatic bis(ether anhydride)s are prepared from the hydrolysis of the reaction product of a nitro-substituted phenyl dinitrile with a metal salt of a dihydroxy aryl compound in the presence of a dipolar aprotic solvent.

Patent
W. W. Kaeding1
01 Nov 1974
TL;DR: In this article, a process for the production of aliphatic amines by reaction of a C 1 -C 5 alcohol or ether with ammonia in the presence of a catalyst comprising a crystalline aluminosilicate having the structure of ZSM-5, ZSM 11 or ZSM 21 was described.
Abstract: Process for the production of aliphatic amines by reaction of a C 1 -C 5 alcohol or ether with ammonia in the presence of a catalyst comprising a crystalline aluminosilicate having the structure of ZSM-5, ZSM-11 or ZSM-21, said reaction being effected at a temperature between about 300° and about 500° C., a pressure between atmospheric and 1000 psig with the relative feed rates, expressed in grams per hour, of (1) alcohol or ether and (2) ammonia being within the approximate range of 1:1 to 5:1.

Journal ArticleDOI
TL;DR: In this paper, it was shown that the optical spectra of tetrahydrofuran can be rationalized in terms of tight and loose ion pair-crown ether complexes.
Abstract: Bathochromic shifts observed in the optical spectra of alkali picrates in tetrahydrofuran on addition of crown ethers and bis-(crown ethers) can be rationalized in terms of tight and loose ion pair-crown ether complexes.

Journal ArticleDOI
TL;DR: In this paper, the synthesis of bis[trimethylsilyl)methyl]zinc, tris[trimsilyl]methyl]aluminium-diethyl ether (1/1), and bis(neopentyl)zinc is described.
Abstract: Synthesis of bis[(trimethylsilyl)methyl)]zinc, tris[(trimethylsilyl)methyl]aluminium–diethyl ether (1/1), and bis(neopentyl)zinc is described. Interaction of the first two compounds with tantalum pentachloride affords (Me3SiCH2)TaCl4, (Me3SiCH2)2TaCl3, and (Me3SiCH2)3TaCl2, and with NbCl5, (Me3SiCH2)3NbCl2. Bis(neopentyl)zinc reacts similarly. Adducts of the zinc, niobium, and tantalum alkyls with amines are also described.

Journal ArticleDOI
TL;DR: It could be proved that every hydroxyl group in a steroid could be transformed into its silyl ether depending on the sily lating mixture used, and also the possibility of using them for structure analyses.

Patent
07 Jan 1974
TL;DR: In this article, the authors provided catalysts consisting essentially of a catalyst system for the ring-opening polymerization of cyclic olefins consisting of (1) a tungsten or molybdenum compound; (2) an organo-aluminum compound; and (3) an ether of vinyl alcohol, of allyl alcohol, or of 2-butene-1-4-diol, the molar ratio of component (1), to component (2), being less than 1 : 1 and themolar ratio (1, to component
Abstract: For the production of polyalkenamers there are provided catalysts consisting essentially of a catalyst system for the ring-opening polymerization of cyclic olefins consisting essentially of (1) a tungsten or molybdenum compound; (2) an organoaluminum compound; and (3) an ether of vinyl alcohol, of allyl alcohol, or of 2-butene-1,4-diol, the molar ratio of component (1) to component (2) being less than 1 : 1 and the molar ratio of component (1) to component (3) being less than 100 : 1. The catalyst system may also contain a compound containing one or more hydroxyl or sulfhydryl groups in a molar ratio to component (1) of about 0 : 1 to 2 : 1, respectively.

Journal ArticleDOI
TL;DR: Ether extracts of urine from patients treated with mitotane (o,p'-DDD) were methylated with diazomethane, and five derivatives of metabolites were detected and identified by comparison of GLC retention times, mass spectra, and IR spectra with synthetic reference compounds.

Journal ArticleDOI
TL;DR: In this paper, the characterization of benzene-, butane-, and methane-boronate trimethylsilyl ether derivatives of some common carbohydrates has been investigated by a combination of high- and low-resolution mass spectrometry.

Patent
28 Aug 1974
TL;DR: A graft copolymer is prepared by graft polymerizing 20 to 200 parts by weight of a styrene type compound on an oligophenylene ether with a polymerization degree of 60 to 90.
Abstract: A novel graft copolymer composition comprising 30 to 90 wt. % of a graft copolymer containing substantially no polyphenylene ether homopolymer and 10 to 70 wt. % of a styrene type compound polymer having a number average molecular weight in the range from 50,000 to 200,000. The graft copolymer is prepared by graft polymerizing 20 to 200 parts by weight of a styrene type compound on an oligophenylene ether with a polymerization degree of 60 to 90. The composition has excellent resistance to creep.

Journal ArticleDOI
TL;DR: Colneleic acid is an unsaturated ether fatty acid derived from linoleic acid via a lipoxygenase-mediated enzyme pathway that is degraded by an enzyme in potato tubers which is heat-labile and non-dialysable and by a model system containing catalytic amounts of Fe(2+) ions.
Abstract: Colneleic acid is an unsaturated ether fatty acid derived from linoleic acid via a lipoxygenase-mediated enzyme pathway. It is degraded (a) by an enzyme in potato tubers which is heat-labile and non-dialysable and (b) by a model system containing catalytic amounts of Fe(2+) ions. Both enzyme- and Fe(2+)-catalysed systems have similar properties with respect to pH optima (pH5.0-5.5), oxygen requirement (0.6-0.7 mol of O(2) consumed/mol of ether degraded), inhibitors and reaction products. An unstable product breaks down to C(8) and C(9) carbonyl fragments. Both systems are inhibited by low concentrations of antioxidants (e.g. 5mum-butylated hydroxytoluene) and some chelating agents (e.g. 5mum-diethyldithio-carbamate). The model system is strongly inhibited by metal ions, particularly Cu(2+) and Fe(3+), at 20mum. Hydrogen peroxide and haemoproteins do not substitute for the enzyme or Fe(2+) ions but the non-haem iron protein, ferredoxin, does catalyse the degradation.