Showing papers on "Ether published in 1973"

Stabilisation of metals in a low co-ordinative environment using the bis(trimethylsilyl)methyl ligand; coloured SnII and PbII alkyls, M[CH(SiMe3)2]2

Abstract: (Me3Si)2CHLi and SnCl2 in ether at 0° give Sn[CH(SiMe3)2]2, which is diamagnetic at room temperature and behaves chemically as a singlet ‘stannylene’, yielding complexes such as R2SnM′(CO)5(M′= Cr or Mo)

Synthesis of some novel trifluoromethanesulfonates and their reactions with alcohols

Abstract: Allyl triflate, propargyl triflate, pentyl triflate, 2-(2-fluoro-2,2-dinitroethoxy)ethyl triflate, 2-fluoro-2,2-dinitroethyl triflate, and 1,2,3-propanetritriflate were prepared from the alcohols using triflic anhydride and pyridine. 1,4-Butaneditriflate was formed from tetrahydrofuran and triflic anhydride. In the presence of potassium carbonate, pentyl triflate, allyl triflate, propargyl triflate, 1,4-butaneditriflate, and 2-( 2-fluoro-2-2-dinitroethyoxy)ethyl triflate reacted in chlorinated hydrocarbon solvents at ambient temperature with 2-fluoro-2,2dinitroethanol to give the corresponding ethers, without skeletal rearrangement. l12,3-Propanetritriflate underwent monosubstitution and elimination to yield 3-( 2-fluoro-2,2-dinitroethoxy)-2-propenyl triflate. Pentyl triflate and 2,2,2-trifluoroethanol gave pentyl 2,2,2-trifluoroethyl ether. When sodium sulfate was used instead of potassium carbonate to scavenge liberated triflic acid, pentyl triflate and 2,2-dinitropropanol gave a mixture of the 1-, 2-, and 3-pentyl ethers. Under these conditions, 2-fluoro-2,2-dinitroethanol, 2,2-dinitropropanol, and 2,2,2-trinitroethanol, as well as pentanol, reacted with isopropyl triflate to give the corresponding isopropyl ethers. Allyl triflate was allowed to react similarly with 2,2-dinitropropanol, 2,2,2-trinitroethanol, and 2,2-dinitro-1,3propanediol to give the allyl ethers. The high reactivity of the trifluoromethanesulfonate (triflate) group in solvolysis and displacement reactions has been the subject of a number of recent investigations. Thus, methyl and ethyl triflates were reported to undergo solvolysis more than lo4 times as fast as the corresponding tosylate~.~~~ The use of the triflate leaving group in otherwise unreactive polycyclic systems has extended the range of solvolysis reaction^,^-^ and vinyl triflates have been used extensively in studies of vinyl ~ations.~-~O Xo attempts have been reported, however, to prepare a triflate ester more reactive than the ethyl derivative. Such extremely reactive alkylating agents would be expected to extend the range of weakly nucleophilic reagents that can be alkylated. The triflates prepared in this work are shown in Table I. Most of these compounds were synthesized from the corresponding alcohols by the commonly used4 triflic anhydride-pyridine method. Methylene chloride and carbon tetrachloride were used as solvents. Methyl triflate, because of its low boiling point, was prepared conveniently, from dimethyl sulfate by a procedure previously used for the corresponding fluorosulfonate.'l The reaction of tetrahydrofuran with triflic anhydride gave 1,4-butaneditriflate1 a reaction similar to ring openings with mixed sulfonic-carboxylic anhydrides. l2 This ditriflate and l12,3-propanetriflate, prepared from glycerol, are the first reported polyfunctional examples. Allyl triflate, propargyl triflate, and isopropyl triflate were not sufficiently stable for elemental analysis and were characterized by spectral data, described in

Method for making polyetherimides and products produced thereby

Abstract: A method is provided for making polyetherimides involving the reaction of aromatic bis(ether anhydride)s and organic diamines in the presence of a phenolic solvent. The resulting polyetherimide-phenolic solvent mixture can be employed as a wire coating enamel.

Umlagerung von Allyl‐aryläthern und Allyl‐cyclohexadienonen mittels Bortrichlorid

Abstract: Allyl aryl ethers which have no strongly electron attracting substituents undergo a charge-induced [3 s, 3 s] sigmatropic rearrangement in the prescence of 0.7 mole boron trichloride in chlorobenzene at low temperature, to give after hydrolysis the corresponding o-allyl phenols (Tables 1 and 2). The charge induction causes an increase in the reaction rate relative to the thermal Claisen rearrangement of ∼1010. With the exception of allyl 3-methoxyphenyl ether (5), m-substituted allyl aryl ethers show similar behaviour (with respect to the composition of the product mixture) to that observed in the thermal rearrangement (Table 3). The rearrangement of allyl aryl ethers with an alkyl group in the o-position, in the prescence of boron trichloride, yields a mixture of o- and p-allyl phenols, where more p-product is present than in the corresponding product mixture from the thermal rearrangement (Table 4). This ‘para-effect’ is especially noticeable for o-alkylated α-methylallyl aryl ethers (Table 5 ). With boron trichloride, 2,6-dialkylated allyl aryl ethers give reaction products which arise, in each case, from a sequence of an ortho-Claisen rearrangement followed by a [1,2]-, [3,3]- or [3,4]-shift of the allyl moiety (Tables 6 and 7). Ally1 mesityl ether (80), with boron trichloride, gives pure 3-ally1 mesitol (95). From phenol, penta-ally1 phenol (101) can be obtained by a total of five O-allylations followed by three thermal and two boron trichloride-induced rearrangements. The sigmatropic rearrangements of the ethers studied, using D- and 14C-labelled compounds, are collected in scheme 2; only the reaction steps indicated by heavy arrows are of importance. With protic acids, there is a [3,3]-shift of the allyl group in 6-allyl-2,6-disubstituted cyclohexa-2,4-dien-l-ones, while with boron trichloride the [3,3]-reaction is also observed along with the much less important [1,2]- and [3,4]-transformations (Table 8). 4-Allyl-4-alkyl-cyclohexa-2,5-dien-1-ones give only [3,3]-rearrangements with boron trichloride (Table 9). As expected, the naphthalenone 112, which is formed by allowing boron trichloridc to react for a short time with allyl (1-methyl-2-naphthyl) ether (111), undergoes only a [3,4] rearrangement (Scheme 3). Representations of how, in our opinion, the complex behaviour of allyl aryl ethers and allyl cyclohexadienones under the influence of boron trichloride, can be rationalized are collected together in Schemes 4 and 5. In the last part of the discussion section, the steric factors leading to the appearance of the ‘para-effect’, are dealt with (Scheme 6).

The Preparation and Chemistry of Dicationically Active Polymers of Tetrahydrofuran

Abstract: The anhydrides of the very strong acids, CF 3 SO 3 H and FSO 3 H, polymerize tetrahydrofuran (THF) to give a living polyether having cationic activity at each chain end. The surprising fact that both chain ends are cationically active necessitates the postulation of a reaction mechanism wherein the YSO,-ester end group (Y=CF 3 or F) formed as an intermediate in the polymerization generates an oxonium ion by a subsequent O-alkylation reaction involving either a THF molecule or a nearest neighbor ether group of the polymer chain. Kinetic studies of polymerizations involving (CF, SO,) 2 0 and the bis-ester, CF 3 SO 3 —C 4 H 5 —O 3 SCF 3 , as initiators indicate that chain growth is much faster where an oxonium ion rather than an ester is the end group. The chemistry of poly-THF dications is discussed. These are strong alkylating agents which make possible the facile preparation of unusual copolymers, block copolymers, and functionally terminated polymers.

Multi-purpose cleaning concentrate

Abstract: A water miscible cleaning composition contains: A GLYCOL ETHER SUCH AS ETHYLENE GLYCOL MONOBUTLY ETHER, DIETHYLENE GLYCOL MONOBUTYL ETHER, ETHYLENE GLYCOL MONOMETHYL ETHER, ETHYLENE GLYCOL MONOETHYL ETHER, DIETHYLENE GLYCOL MONOMETHYL ETHER OR DIETHYLENE GLYCOL MONOETHYL ETHER; A GLYCOL SUCH AS PROPYLENE GLYCOL, DIETHYLENE GLYCOL, HEXYLENE GLYCOL (2-METHYL-2, 4 PENTANEDIOL), TRIETHYLENE GLYCOL OR DIPROPYLENE GLYCOL; A MONOHYDROXY ALCOHOL SUCH AS ISOPROPANOL, N-PROPANOL OR ISOBUTANOL; AMMONIUM HYDROXIDE; AND AN AMINE, SUCH AS TRIETHANOLAMINE, MONOETHANOLAMINE, DIETHANOLAMINE, MONOISOPROPANOLAMINE, DIISOPROPANOLAMINE, TRIISOPROPANOLAMINE, MONOMETHYLAMINE, DIMETHYLAMINE, ETHYLENEDIAMINE, PROPYLENEDIAMINE, CYCLOHEXYLAMINE, DIETHYLETHANOLAMINE, ETHYL DIETHANOLAMINE, OR MORPHOLINE; AND A SYNTHETIC DETERGENT.

Effect of electrodeless glow discharge on polymers

Abstract: The effects of gas plasma generated by electrodeless (inductive coupling) glow discharge on polymers were investigated as functions of gas pressure, discharge power, exposure time, and type of plasma gas. A remarkable similarity between the plasma susceptibilities of low molecular weight organic compounds and polymers was observed; i.e., polymers which have ether, carbonyl, ester, or carboxylic acid attached to a nonaromatic structure are very susceptible to plasma. The weight loss was proportional to the exposure time and exposed area. The discharge power and type of gas were found to have a great influence on both the rate of weight loss and the morphology of the exposed surface. The predominant effect of plasma on polymers was found to be degradation (manifested by weight loss). The crosslinking effect was found to be marginal with many polymers; however, significant crosslinking was observed with double bond-containing polymers. The crosslinking was examined by swelling the treated films. With copolymers of styrene–butadiene, 4-vinylpyridine–butadiene, methacrylic acid-butadiene, and acrylic acid–butadiene, the crosslinking was greatly dependent on the discharge power, the butadiene content of the copolymers, and the exposure time. Both degradation and crosslinking by gas plasma were generally limited to the exposed surface; however, the propagation of crosslinking in the direction of thickness was observed with copolymers of styrene–butadiene. The plasma of organic vapor also cause degradation of plasma-susceptible polymers, particularly at high wattage, although the deposition of polymer occurs simultaneously.

Divinyl Ether-Maleic Anhydride (Pyran) Copolymer used to demonstrate the Effect of Molecular Weight on Biological Activity

Abstract: DIVINYL ether and maleic anhydride form a 1:2 copolymer, which is reported to have the structure shown here1. It is commonly known as pyran copolymer, although we prefer to call it DIVEMA, an acronym for divinyl ethermaleic anhydride. It has been designated as NSC 46015 by the National Cancer Institute.

Method for making aromatic bis(ether anhydride)s

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.

Die durch Silberionen katalysierte Umlagerung von Propargyl‐phenyläther

Abstract: It is known that propargyl-phenylethers rearrange at about 200° to 2 H-chromenes [1–4]. It is shown that this rearrangement occurs in benzene or chloroform at lower temperatures (20–80°) in the presence of silver-tetrafluoroborate (or-trifluoracetate). The ethers examined are presented in Scheme 1. Thus in chloroform at 61° in the presence of AgBF4, phenyl-propargylether (3) yields 2 H-chromene (13). With 0.78 molar equivalents AgBF4 in benzene at 80° the same ether 3 yields a 3:1 mixture of 2-methyl-cumaron (14) and 2 H-chromene (13). From 1′-methylpropargyl-phenylether (4) and 2′-butinyl-3,5-dimethylphenylether (5) under similar conditions the corresponding chromenes 16 and 17 resp. are obtained. Rearrangement of propargyl- and 2′-butinyl-1-methyl-2-naphthylether (6 and 7 resp.) in benzene at 80° in the presence of AgBF4 gives the corresponding allenyl-naphthalenones 18 and 19 resp. Treatment of propargyl- and 2′-butinyl-mesityl-ether (8 and 9 resp.), and propargyl- and l′-methylpropargyl-2,6-dimethyl-phenylether (10 and 11 resp.) in benzene at 80° with AgRF, yields as the only product the corresponding 3-allenyl-phenols 21, 22,24 and 25 (Scheme 3). It is shown that in the presence of μ-dichlor-dirhodiuni (1)-tetracarbonyl in benzene a t 80° the ether 4 rearranges to 2-methyl-2H-chromene (16). However with this catalyst the predominant reaction is a cleavage to phenol. No reaction was observed when ethers 3 and 12, (Scheme 7 ) were treated with the tris-(trimethylsily1)-ester of vanadic acid in benzene a t 80° (see also [8]). By analogy with the known mechanism for thc silver catalysis of the reversible propargylesterl/allenylester rearrangement [S], the silver (1)ion is assumed to form a pre-equilibrium π-complex with the C, C-triplebond of the substrate. This complex then undergoes a [3s, 3s]-sigmatropic rearrangement (Scheme 2). In the case of the others 6, 7 and 12 the resulting allenyldienones were isolated. The 2,G-dimethyl substituted ethers 8, 9, 10 and 11 resp. first give the usual allenyl- dienones (Scheme 3). These then undergo a novel silver catalysed dienon-phenol-rearrangement (Sclzenzu4) to give the 3-allenylphenols 21, 22, 24 and 25. Thc others 3, 4 and 5 with free ortho positions presumably rearrange first to the non-isolated 2-allenyl-phenols 15, 42 and 43 resp.(Scheme 7). These then rearrange, either thermally or by silver (1)ion catalysis to the 2H-chromenes 13,16 and 17 resp. The rate of the rearrangement of 2-allenylphenol (15) to 13 at room temperature in benzene or chloroform is approximately doubled when silver ions are present as catalyst.

Acetylene substituted polyamide oligomers

Abstract: 1. A COMPOUND HAVING THE FORMULA CHEMICAL STRUCTURE: HC*C-R''-((-CO-N(-)-CO-)>R" R"<(-CO-N(-R''-C*CH)-CO-) WHEREIN R IS POLY(ARYLENE ETHER) OR POLY(ARYLENE THIOETHER), R'' IS ARYLENE OR DIARYLENE ETHER, N IS AN AVERAGE FROM 1 TO ABOUT 10, AND R" IS -(4,5-DI(-)-1,2-PHENYLENE)- OR -(4-(3,4-DI(-)-PHENYL-S-)-1,2-PHENYLENE)- AND X IS C=O, CH2, O. S, OR A BOND.

Silylmethyl and related complexes. Part I. Kinetically stable alkyls of titanium(IV), zirconium(IV), and hafnium(IV)

Abstract: Complexes of the type Cp2M(CH2M′Me3)2(Cp =π-C5H5; M = Ti, Zr, or Hf; M′= Si or Ge) have been prepared from Me3M′CH2Li, or less satisfactorily from the Grignard reagent, and Cp2MCl2 in ether. Cp2Zr(Cl)CH2SiMe3 was prepared via Me3SiCH2MgCl in ether–methylene chloride. Isoleptic complexes (RnMe3 –nSiCH2)4M (M = Ti, Zr, or Hf; n= 0–2; R = Ph or PhCH2) have been prepared by the reaction of MCl4 with Me3SiCH2Li in ether or hexane, RnMe3 –nSiCH2MgCl in ether, or (RnMe3 –nSiCH2)2Mg in hexane. The complexes are thermally more stable than their methyl analogues; oxidative stabilities of the isoleptic compounds correlate with the degree of steric shielding at the metal centre. Spectroscopic data are provided, and the reactions of the isoleptic compounds with water, iodine, and acetylacetone are described.

Reactions of dialkylaurate(I) with electrophiles: synthesis of trialkylgold(III) compounds

Abstract: The formation of new dialkylaurate(I) species from alkylgold(I) complexes and alkyl-lithium is described. Lithium dimethyl(triphenylphosphine)aurate(I) is stable only in ether solutions, but the crystalline bis-pyridine analogue can be isolated. A variety of mixed primary, secondary, and tertiary dialkylaurate(I) analogues can also be prepared in situ and reacted directly with alkyl halides in the convenient synthesis of trialkylgold(III) complexes. The stereospecific synthesis of trans- or cis-alkyldimethyl(triphenylphosphine)gold compounds is possible from the reaction of dimethyl(triphenylphosphine)aurate(l) and alkyl halide or cis-dimethyliodo(triphenylphosphine)gold and alkyl-lithium, respectively. Bromination and protonolysis of dialkylaurate(I) proceed readily at 0 °C. The lack of selectivity in the cleavage of mixed alkylmethylaurate(I) with hydrogen chloride suggests that it proceeds by oxidative addition, in contrast with the direct proton transfer to the alkyl ligand as in many other electrophilic cleavages. Unsuccessful attempts to add alkenes and co-ordinated olefinic ligands to dialkylaurate(I) are described.

Hydroxyl or thiol terminated telomeric ethers

Abstract: Hydroxyl or thiol terminated alkylene ether telomers varying from liquids to thermoplastic solids and composed of one or more telomer moieties from cyclic ether taxogen joined through a carbon atom to a telogen moiety are prepared by telomerization of cyclic ether monomer with a primary or secondary aromatic amine as a telogen in the presence of catalyst of the double metal cyanide complex class. As a specific example, a hydroxyl terminated telomer is prepared by telomerization of propylene oxide with aniline using zinc hexacyanoferrate-diglyme complex as the telomerization catalyst.

Piperidine derivatives and their use as stabilizers

Abstract: Piperidine derivatives having the formula ##SPC1## Wherein R' represents an alkyl group, a substituted alkyl group, an acyl group, an alkoxycarbonyl group, a substituted alkoxycarbonyl group, an amino group, a substituted amino group, or nitroso group; X represents oxygen atom or sulfur atom; Y represents oxygen atom, sulfur atom or a group of the formula = N -- R" in which R" is hydrogen atom, an alkyl group or a substituted alkyl group; Z represents oxygen atom or a group of the formula >N -- R'" in which R'" is hydrogen atom, an alkyl group or a substituted alkyl group; n is an integer of 1 through 4 inclusive; and R represents, when n is 1, an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, a cycloalkyl group, an alkoxycarbonyl group, a substituted alkoxycarbonyl group, a substituted phosphino group or a substituted phosphinyl group, when n is 2, an alkylene group, an alkenylene group, an arylene group, a substituted arylene group, an aralkylene group; an alkylenediphenylene group, a bis-(acyloxyalkylene) group, an alkylene-bis-(oxycarbonylalkyl) group, a dialkylene ether group or a diphenylene ether group, when n is 3, an alkanetriyl group, a tris(acyloxyalkylene) group, an alkane-tris(oxycarbonylakyl) group or a group of the group ##SPC2## In which p is an integer of 1 through 8 inclusive, and, when n is 4, an alkanetetrayl group, a tetrakis-(acyloxyalkylene) group or an alkane-tetrakis-(oxycarbonylalkyl) group. The piperidine derivatives (I) of this invention are prepared in various manners and useful as stabilizers for synthetic polymers against thermal- and photo-deterioration thereof.

The Chemisorption of Anisole on Cu(II) Hectorite

Abstract: The sorption of anisole and some related aromatic ethers on the interlamellar surfaces of Cu(II) hectorite has been investigated by i.r. and e.s.r, spectroscopy. In addition to physical adsorp- tion, anisole forms two distinct types of Cu(II) complexes which are analogous to the type 1 and II species previously reported for benzene-Cu(II) smectite systems. These complexes can be trans- formed to type I and II complexes of 4,4'-dimethoxybiphenyl. Possible mechanisms are proposed for the oxidation process. Butyl phenyl ether formed a type II complex with Cu(II)-hectorite, no dimerization reaction was noted in this system. Phenyl ether and benzyl methyl ether form a type I ~r complex with Cu(II)-hectorite. type II analog was noted. E.S.R. spectra of each of the type II ether-Cu(II)-hectorite systems showed a sing/e, narrow band with g near the value expected for a "free spinning" electron. The type I phenyl ether and benzyl methyl ether complexes also exhibited this e.s.r, band. Ag(I) hectorite adsorbs anisole by forming exclusively a type I complex. Na(I) and Co(II) hectorite adsorb anisole by physical means only, indicating association with the silicate surface.

A study of hydroxyl participation in acyclic epoxide systems. Acid-catalysed rearrangements of trans- and cis-3,4-Epoxypentan-1-ols, 4,5-Epoxyhexan-1-ols, and 5,6-Epoxyheptan-1-ols

Abstract: The acid-catalysed rearrangements of trans- and cis-4,5-epoxyhexan-1- ols and 5,6-epoxyheptan-1-ols demonstrate a preference for cyclic ether formation: tetrahydrofuran > tetrahydropyran > oxepan. The ether products arise by intramolecular hydroxyl displacement of the epoxide oxygen with inversion of configuration. Reactions of trans- and cis- epoxypentan-1-ols give a mixture of trans- and cis-2-methyl-tetrahydro- furan-3-ols (8) and (9). From each epoxide one methyltetrahydrofuranol must arise by nucleophilic displacement of the secondary epoxide oxygen with retention of configuration.

The Use of Polymer Supports in Organic Synthesis. II. The Syntheses of Monoethers of Symmetrical Diols

Abstract: An insoluble polymer support system was used as a unique method of blocking one functional group of a completely symmetrical difunctional compound. The monotetrahydropyranyl and monotrityl ethers of the symmetrical diols, HO—(CH2)n—OH, where n = 2,4,6,8, and 10, were prepared. Reaction conditions for the preparation of the monotetrahydropyranyl ether of 1,10-decanediol were optimized.

Bacterial Cleavage of an Arylglycerol-β-Aryl Ether Bond

Abstract: The first known cleavage by a bacterium of an arylglycerol-β-aryl ether linkage, the most common intermonomer linkage in lignin, is described.

Composition of a polyphenylene ether and a block copolymer of a vinyl aromatic compound and a conjugated diene

Abstract: There are provided compositions comprising (a) a polyphenylene ether, (b) an elastomeric block copolymer and (c) a high impact rubber modified polystyrene resin or a blend of a high impact rubber modified polystyrene resin and a homopolystyrene resin.