JPS63264147A - Catalyst composition and its use - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION It is well known that sulfuric acid catalyzes various organic reactions. It is also known to combine urea (the chalcogen compound useful in the present invention) and sulfuric acid to form adducts, including monourea-sulfate adducts and diurea-sulfate adducts, e.g. rVerslag Akad,
Wellenschappen J 22.573-4
(“Chemical Abstracts J 8.2346 (19
14) describes the formation of urea from certain compounds and oxalic acid, acetic acid, hydrochloric acid, nitric acid and sulfuric acid. L, H, Dal-atan
Mr. “Three component system of urea and acid 1. Urea, nitric acid and water ■, urea, sulfuric acid and water ■, urea.

Oxalic acid and water J: rJAC≦” dish, 549-53 (
(1934) describes the phase relationship between a solid phase and a saturated solution containing urea and sulfuric acid at 10°C and 25°C. Sulfur Association “Sulfur Association Bulletin” NcLl
(1964): Addition of the Plant Nutrient Sulfur to Fertilizers'' describes the reaction of urea with sulfuric acid to produce two complexes of ``urea sulfate'', which are useful fertilizers.

Methods for making certain compounds of urea and sulfuric acid are described in US Pat. Nos. 4,310,343 and 4,116,664.

A wide variety of organic conversions are catalyzed by the proton-donating ability of strong acids; such reactions have been extensively studied and widely reported in the literature, e.g. Kirku-Osmer Encyclopedia of Chemical Technology, 3rd edition, J.
Ohn Wiley and 5ons Publishers, New York, USA (1980) describes various organic compounds catalyzed by strong acids, including mineral acids, Friedel-Crafts catalysts, transition metal halides such as conjugated Friedel-Crafts catalysts, etc. The reaction is described. In the above-mentioned "Kirku Osmer Encyclopedia", page 5@, page 33, acid-catalyzed reactions (acid-catalyzed reactions)
zed reactions) are defined as reactions in which protons are transferred from the catalyst to the reactants, thereby immediately leading to the reaction under consideration (conversion to an unstable state). Although proton donation mechanisms may or may not be considered for the reactions that occur in all acid-catalyzed reactions, strong acids
dition reductive add
ition) *Esterification.

transesterification, hydrogenation, isomerization (including racemization of optical isomers), hydrolysis and alcoholysis.

Alkylation, olefin polymerization, Friedel-Crafts reaction, demetalization of organic substances (de-+5 etalbzati
on).

and facilitates many reactions including nitration and others. Strong acids known to promote such acid-catalyzed organic reactions include, for example, sulfuric acid; nitric acid; hydrochloric acid; transition metal halides, including the so-called Friedel-Crafts catalysts, such as aluminum, gallium, boron,
halides such as titanium, vanadium, and tin; and conjugated Friedels, known as Brønsted-Lewis superacid mixtures such as mineral acid adducts of transition metal halides (Kirku-Othmer Dictionary, Vol. 11, p. 295). -Crafts catalysts may be mentioned.

All known strong acid catalysts and processes involving the action of such strong acid catalysts for the promotion of acid-catalyzed organic reactions have one or more drawbacks.

For example, strong mineral acids generate undesirable by-products, destroy organic feeds or products, and/or promote side reactions that consume or deactivate the catalyst.

Sulfuric acid is a strong sulfating, sulfonating, oxidizing and dehydrating agent, and due to its activation it is consumed by side reactions involving these mechanisms in many organic reactions.

Additionally, sulfonation and oxidative activation of sulfuric acid can be performed on organic feedstocks and/or oxidative activation. sulfonates and oxidizes the product. 11 (11) Disadvantages also exist with other strong mineral acids such as hydrochloric acid and nitric acid. Hydrochloric acid chlorinates the reactants, thereby consuming the feedstock and producing undesirable chlorinated by-products. oxidizes and/or nitrates organic compounds. Hydrofluoric acid fluorinates organic reactants and products. Transition metal halides, including Friedel-Crafts catalysts, separate this from water and reducing agents. They are difficult to handle when necessary and such catalysts hydrogenate organic feedstocks and products.

Accordingly, there is a need for improved methods of conducting acid-catalyzed organic reactions, and for improved acid catalysts for use in such reactions that promote the desired acid-catalyzed organic reactions. The objective is to reduce or eliminate side reactions normally associated with

Therefore, the main object of the present invention is to provide a new process for the acid-catalyzed conversion of organic compounds.

Another object of the invention is the acid-catalyzed reaction of organic compounds (a
The object of the present invention is to provide a new method for performing a cid-catalyzed reaction in the presence of a composition consisting of sulfuric acid.

Another object of the present invention is to provide a new acid catalyst consisting of sulfuric acid that is effective in carrying out acid-catalyzed organic reactions.

Another object of this invention is to provide new compositions useful for carrying out acid-catalyzed organic reactions.

Another object of the invention is to provide a new catalyst consisting of sulfuric acid which possesses improved activity in the presence of lipophilic materials.

Another object of the invention is to provide a new method for catalyzing organic reactions with sulfuric acid.

Another object of the invention is to provide a new method for oxidative addition of organic compounds.

Another object of the invention is to provide a new method for the reductive addition of organic compounds.

Another object of the present invention is to provide novel sulfuric acid-containing compositions useful for carrying out organic reactions.

Another object of the invention is to provide a new method for esterifying and transesterifying organic compounds.

Another object of the invention is to provide a new method for hydrogenating organic compounds having olefinic unsaturation.

Another object of the invention is to provide a new method for isomerizing organic compounds.

Another object of the present invention is to provide new methods for hydrolysis, alcoholysis, thiolosis and amination of organic compounds.

Another object of the present invention is to provide a new method for alkylating edible compounds.

It is an object of the present invention to provide a new method for polymerizing olefin compounds.

Another object of the invention is to provide new conjugated Friedel-Crafts catalysts.

Another object of the invention is to provide new Friedel-Crafts catalytic organic compounds.

Another object of the present invention is to provide a new method for demetallizing organic compounds.

Yet another object of the present invention is to provide a new method for nitrating organic compounds.

Briefly, the present invention provides (1) novel surfactant-containing catalyst compositions suitable for promoting acid-catalyzed organic reactions;
2) Novel conjugated Friedel-Crafts acid catalysts suitable for promoting acid-catalyzed organic reactions; (3) Chalcokene-containing compounds. Sulfuric acid, and 1 useful in carrying out organic reactions
Another object of the present invention is to provide a novel reactant-containing composition containing two or more kinds of reactants, and (4) a novel method for carrying out an acid-catalyzed reaction.

The present invention has found that compositions comprising one or more chalcogen-containing compounds and sulfuric acid, where the molar ratio of chalcogen compound to sulfuric acid is less than or equal to 2, are extremely useful as catalysts, particularly for organic reactions. Within this range of zero molar ratios, at least one part of the sulfuric acid forms the monourea adduct of sulfuric acid, which is an active acid catalyst useful herein. Useful chalcogen-containing compounds have the following empirical formula: R1-C-R.

(In the formula, X represents chalcogen, each of R1 and R2 represents hydrogen, NRJ-a or NR5, at least one of R1 and R2 represents a group other than hydrogen, and R5
and R4 each represents hydrogen or a monovalent organic group,
and R2 represents a divalent organic group).

Among these, the novel catalyst of the present invention is a chalcogen compound-
The composition contains a sulfuric acid component as well as a surfactant and/or a solvent. In particular, the catalyst is useful for promoting chemical reactions involving relatively lipophilic organic materials. This is because the surfactant and/or solvent enhance the activity of the chalcogen compound-acid component toward the lipophilic material.

The present invention also provides a conjugated Friedel-Crafts catalyst that includes a combination of the above-mentioned chalcogen compound-sulfuric acid component, a surfactant, and one or more transition metal halides, or does not contain the above-mentioned surfactant. do.

The present invention also provides a novel reactant-containing composition that contains the chalcogen compound-sulfuric acid component, a surfactant, and one or more reactants used in the organic reaction, or does not contain the surfactant. provide.

The novel process of the present invention involves the acid-catalyzed reaction of one or more organic compounds in the presence of the catalysts described above. In particular, solvent- and/or surfactant-containing catalysts are useful in many acid-catalyzed organic reactions, especially those acid-catalyzed organic reactions where lipophilic, i.e. hydrophobic, materials are present. and solvents were confirmed to enhance the activity of chalcogen-acid components towards lipophilic substances. Similarly, the new conjugated acid catalysts can be used in the new process of the present invention.

In particular, the novel process of the present invention involves the conversion of at least some organic material by the acid catalytic activity of sulfuric acid. The novel process therefore encompasses all acid-catalyzed organic reactions catalyzed by sulfuric acid, such as: (a) oxidation of one or more organic compounds in the presence of an oxidizing agent; ) reduction of l or more organic compounds by reaction with a reducing agent such as hydrogen; (C) l or 2 by reaction with water and/or one or more alcohols and/or thiols;
Hydrolysis of one or more organic compounds; (d) Oxidative addition of one or more organic compounds by reaction with an oxidizing agent; (e) Reductive addition of an organic compound by reaction with a reducing agent; Esterification of amides, nitriles, carboxylic acids, acyl halides, thiocarboxylic acids and/or carboxylic acid anhydrides by reaction with and/or thiols: Hydrogenation; (c) Alkylation of an organic compound by reaction with an organic alkylating agent having at least one carbon-carbon olefinic bond; 0) Polymerization of an organic compound having olefinic unsaturation in the presence of an oxidizing agent; (j ) Friedel-Crafts reactions of organic compounds with hydrocarbyl halogen compounds; (k) isomerization of hydrocarbons having from 4 to about 20 carbon atoms per molecule; (1) organometallic compounds by reaction with water and/or alcohols; demetallation of organic compounds; and - nitration of organic compounds by reaction with nitrating agents such as nitric acid.

The methods and compositions of the present invention can eliminate most, if not all, of the disadvantages associated with acid-catalyzed conversion of organic compounds in the presence of sulfuric acid. The chalicogen compound-sulfuric acid component can reduce or completely eliminate the undesirable oxidation, dehydration and sulfonation activities of sulfuric acid that still possess the strong proton-donating ability of the acid. Because of this, the sulfuric acid contained in the chalcogen compound-acid component is not destroyed during the acid-catalyzed organic reaction by sulfonation, oxidation or other reactions associated with sulfuric acid, and at the same time the organic feedstock is free from side effects normally associated with sulfuric acid. All of these benefits include the novel surfactant-containing catalysts and the novel conjugated transition metal, halide catalysts, which are not destroyed or converted into undesirable by-products by the use of all forms of chalcogen compounds used in the process of the present invention. - Present in the sulfuric acid component. Furthermore, catalysts containing solvents and surfactants increase the conversion of organic compounds by the process of the invention, particularly high (wo)
re) exhibit improved catalytic activity for the conversion of lipophilic compounds and organic materials containing lipophilic substances such as fats, waxes and high molecular weight organic materials.

Without wishing to be bound by any particular theory, the addition of sulfuric acid to a compound, such as the chalcogen compounds mentioned above, which can donate electrons to sulfuric acid, suppresses the propensity of the acid for undesirable side reactions. (acid
The strong electron donor that appears to alter the instability of hydrogen
For example, the monourea adduct of sulfuric acid is a selectively active catalyst, and the diurea adduct is a selectively active catalyst, and the diurea adduct is a selectively active catalyst. Virtually inert.

The present invention provides (1) a chalcogen compound-sulfuric acid mixture containing a surfactant that is an effective acid catalyst for promoting organic conversion; (2) a conjugated free compound consisting of a transition metal halide and a combination of the chalcogen compound-acid component described above; Del-
a Crafts catalyst; (3) a composition comprising the above-described novel catalyst of the present invention, a surfactant and one or more reactants useful in organic reactions, or such a composition free of the above-mentioned surfactant; and (4) Provides a method for conducting acid-catalyzed organic reactions, particularly known organic reactions catalyzed by sulfuric acid.

The chalcogen compound-sulfuric acid component useful in the methods of the invention includes a combination of sulfuric acid and one or more certain chalcogen compounds (where the molar ratio of chalcogen compound to sulfuric acid is less than or equal to 2). . Within this molar ratio range, at least a portion of the sulfuric acid is present as a mons-adduct of sulfuric acid. In one example, the chalcogen compound-acid component can optionally contain surfactants, solvents, or other ingredients.

Surfactants and solvents are effective against organic materials, especially fats,
Enhances the activity of acid components on organic materials containing lipophilic components such as oils, waxes, etc.

The chalcogen compound-sulfuric acid component with or without surfactants is cobined with one or more organic or inorganic reactants of interest in the desired organic reaction. form a composition useful for. In other examples, the chalcogen compound-acid component and a surfactant, or the chalcogen compound-acid component without the surfactant, may be mixed with a common transition metal halide catalyst to form a conjugated Friedel-acid component useful in these processes. A Krafts catalyst can be formed.

The process of the invention involves acid-catalyzed conversion of organic compounds. In particular, the process of the present invention can be used for the acid-catalyzed conversion of any organic material that can be converted with a sulfuric acid catalyst without the undesirable side reactions commonly associated with sulfuric acid. Suitable acid-catalyzed reactions include, for example, oxidations, especially oxidative additions: esterification; transesterification; hydrogenation.

Isomerization, including racemization of optical isomers; hydrolysis and alcoholysis by reaction with water, alcohols or thiols; alkylation; olefin polymerization; Friedel-Crafts reactions; demetalization; and nitration. . In the process of the invention, the organic reactant is contacted with the chalcogen compound-sulfuric acid component in the form of a solution in water or other solvent or as a molten mixture of the chalcogen compound and sulfuric acid.

Chalcogen compound - sulfuric acid component is nitric acid and 1 or 2
A reaction product of one or more chalcogen-containing compounds, where the molar ratio of chalcogen compound to sulfuric acid is 2 or less. In such components, at least a portion of the sulfuric acid is present as a mono-adduct of sulfuric acid and a chalcogen compound.

These components are used as a melt in the method of the invention.
Carbon; silica or chalcogen compound-sulfuric acid component as a solution in water or other solvents.

Solid supports such as refractory oxides such as alumina; acidic or basic ion exchange resins; or zeolites such as natural and synthetic aluminosilicates and mixtures of such supports may be used as solids to be impregnated or exchanged. can. The catalyst can also contain optional components such as surfactants and transition metal halides. Other components may also be present that do not substantially nullify the proton-donating activity of the sulfuric acid mono-adduct.

Useful chalcogen-containing compounds have the formula shown below.

R+ CRg (wherein, X represents chalcogen, R1 and R2 are each selected from hydrogen, NR3R4 or NR5, and R3
and R1 represents a group other than hydrogen, P,
and R4 each represent hydrogen or a monovalent organic group,
and Rs represents a divalent organic group), one of the -valent groups R1 and R4 can be hydrogen, and either one or both of R8 and R4 is alkyl, aryl, alkenyl, alkenylaryl, aralkyl, aralkenyl , cycloalkyl, cycloalkenyl, or alkynyl, where such organic group contains no substituents or hydroxy, carboxy.

m8% can be substituted with pendant functional groups such as oxide, thio, thiol or other groups, and the organic group can contain non-cyclic heteroatoms such as oxygen, sulfur, nitrogen, etc. alkdyl
, ardyl, alkendyl
ydyl), alkyndyl,
It can refer to any divalent organic group such as aralkdyl, aralkendyl, which groups include pendant atoms or substituents and/or acyclic or cyclic heterologs as described for R3 and R4. It can contain atoms.

Preferably, R1 and R3 are both groups other than hydrogen, and R1 and R4 are both hydrogen, or about 10
and X is preferably oxygen or sulfur, particularly preferably oxygen.

Such substituents are preferred because of their relatively high chemical stability; particularly preferred chalcogen-containing compounds include urea,
Thiourea, formamide and combinations thereof.

Chalcogen is an element in group Vl-B of the periodic table,
Includes oxygen, sulfur, serine, tellurium and boronium. Oxygen and sulfur are preferred due to low cost availability, low toxicity and chemical activity, with oxygen being particularly preferred.

Chalcogen compound - sulfuric acid component is unreacted (free) sulfuric acid,
Or it can contain a di-adduct of sulfuric acid. Chalcokene compound. The preferred proportions of sulfuric acid and the mono- and di-adducts of sulfuric acid in relation to each other can be conveniently expressed in terms of the chalcokene compound/sulfuric acid molar ratio. This molar ratio is less than or equal to 2 and usually ranges from about 1/4 to about 774, preferably from about 172 to about 372, particularly preferably from about 1 to about 372. A molar ratio ranging from about 174 to about 7/4 may define a composition in which at least 25% of the sulfuric acid is present as a mono-adduct of sulfuric acid. A molar ratio ranging from 172 to about 372 is at least 50
% of sulfuric acid is present as mono-adduct. A most preferred molar ratio of about 1/1 to about 372 defines a composition that is substantially free of uncomplexed sulfuric acid and in which at least 50% of the sulfuric acid is present as a mono-adduct of sulfuric acid. Can be done. The most preferred mixture has a chalcokene compound/sulfuric acid molar ratio of about 171. In such compositions, substantially all of the sulfuric acid is present as a mono-adduct of sulfuric acid, and such compositions contain substantially no uncomplexed sulfuric acid, i.e., mono- or Sulfuric acid that does not complex with chalcogen compounds as a di-addition is not preferred because, when present in significant amounts, sulfuric acid promotes side reactions such as oxidation, sulfonation, dehydration and/or other reactions. However, in general, di-adducts are not detrimental to the performance of the mono-adduct components as acid catalysts for organic reactions, and because of their low or no proton-donating ability, they are not as effective as acid-catalyses. It has little or no activity as a catalyst for organic reactions.

Useful solutions contain a catalytically active amount of the heptadduct of sulfuric acid in a suitable solvent. Extremely low mono-adduct concentration,
For example, a solution (or melt) on the order of about 0.5% by weight is sufficient to promote various acid-catalyzed organic reactions.

However, higher concentrations of mono-adduct are generally preferred. Therefore, the solution usually contains at least 0.5% by weight.
Generally at least 1% by weight, preferably at least about 5%
It may contain % by weight, particularly preferably at least about 10% by weight, of chalcogen compound and sulfuric acid (based on the combined weight of both components). High concentrations of chalcogen compounds and sulfuric acid can obtain increased catalytic activity. for example at least 50% by weight, or 80% by weight
% or more of a mixture of chalcogen compounds and sulfuric acid (in combination)
on))) is usually 0.5 to about 9% of the solution.
0% by weight, generally about 1 to 90% by weight, preferably about 5 to 90% by weight
It accounts for about 90% by weight.

Any solvent suitable for dissolving the chalcogen compound-sulfuric acid component under the reaction conditions can be used. Suitable solvents include, for example, water, dimethyl sulfoxide (DMSO),
) Halogenated hydrocarbons such as dichloromethane, oxygenated hydrocarbons such as methyl ethyl ketone and tetrahydrofuran. Unless the solvent is used as a solvent for the chalcogen compound-sulfuric acid component, the organic feed, intermediate or product, or the organic feed for the urea-sulfuric acid component,
Preferably, it does not react with other moieties used in the acid-catalyzed organic reaction.

When water is used as the sole solvent or as a component of the solvent, at relatively high water concentrations, water displaces the chalcogen compound as an adduct on the sulfuric acid, thereby liberating free sulfuric acid into the system. This process is
The chalcogen compound-sulfuric acid adduct reform can be reversed to remove water from the system. For this reason, preferred compositions and catalyst systems have a H20/(chalcogen compound 10 Hz SOi ) molar ratio of about 5 or less, preferably about 2.5 or less.

Additionally, melts of chalcogen compound-sulfuric acid component-containing compositions having melting points above ambient temperature, e.g., about 70'P, can be used to catalyze acid-catalyzed organic reactions. The active ingredient useful in this example is a solid at ambient temperature and is converted to a melt by heating to an elevated reaction temperature. In this example, the melt is typically at least about 50% by weight, preferably at least about 80% by weight, based on the combined weight of chalcogen compound and sulfuric acid.
Contains % by weight of chalcogen compound-sulfuric acid component. It usually contains at least 20% by weight, generally at least about 50% and preferably about 80% by weight of the preferred heptadduct of sulfuric acid.

The compositions used in the methods of the invention also, although not necessarily, are chemically stable for a significant period of time in the presence of the acid adduct component and in the presence of other components used in the methods of the invention. One or more surfactants may be included.Surfactants include waxes, proteins, ligands, fats, alkanes, high molecular weight acids.

For example, surfactants enhance the activity of acid adducts against almost all non-polar organic compounds, including lipophilic organic materials such as alcohols.
Enhances the activity of liquid acid adduct compositions on cellulosic materials such as waxy cuticle-covered, growing or foraging vegetation. Therefore, the surfactant may be used as described below and in Japanese Patent Application No. 8326/1983 filed by the same applicant as the present application.
No. 4 (filed April 12, 1961), the acid-catalyzed hydrolysis of lipid-containing cellulosic materials and the herbicidal activity of the compositions against growing vegetation.
increase intellectual activity).

The herbicidal activity of the above-mentioned chalcogen compound-sulfuric acid component is demonstrated at least in part by the herbicidal activity of the chalcogen compound-sulfuric acid component.
This may be due to its ability to catalyze the chemical conversion of cellulose and/or other organic compounds in er). As described herein, these chalcogen compound-sulfate components can catalyze reactions involving non-plant organic compounds.

The selected surfactants, in liquid or solid compositions or in the melts produced from solid compositions, have sufficient wetting capacity for the organic material to be converted as required in the production, storage, transport and use of the chalcogen compound-sulfuric acid component. The stability of any surfactant is preferably selected to be sufficiently chemically stable so that it can be maintained over time. and can be easily measured by monitoring by conventional nuclear magnetic resonance (NMR) analytical techniques. NMR can be used to monitor the frequency and magnitude of specific peak characteristics of selected nuclei in surfactants, such as hydrogen nuclei. Stability is indicated when the spectral peak magnitudes and frequencies are connected over a period of 5-6 hours or more. A decrease in peak size or shift in peak frequency associated with a selected nucleus is indicative of instability, ie, alters the arrangement of functional groups in the surfactant molecule.

Stable surfactants include, for example, nonionic surfactants such as alkylphenol polyethyl oxide, anionic surfactants such as long chain alkyl sulfates, and 1-hydroxyethyl-2-heptadecenyl gloxa-1idin. Cationic activators such as

Among these, polyethylene oxide nonionic surfactants are particularly preferred; preferred specific surfactants include nonionic surfactants commercially available under the trade name rT-MIILZ 891J (Thompson-Hayw
ard.

(manufactured by Inc.) can be exemplified.

The surfactant concentration is preferably sufficient to enhance the wetting ability of the chalcogen compound-acid component to the organic material to be added, even at very low surfactant concentrations.
The wetting ability of the acid-adduct component can be enhanced to some extent. Typically, the surfactant concentration when used in the method of the present invention will be at least about 0.05% by weight, generally at least about 0.1% by weight. , preferably at least about 0.2% by weight solution. Surfactant concentrations of about 0.2 to about 1% by weight are suitable for use.

The chalcogen compound-sulfuric acid component combines with the transition metal halide to form the conjugate acid of the acid adduct with the transition metal halide. Transition metal halides such as Friedel-Crafts catalysts and such conjugate acids of transition metal halides used in so-called Ziegler catalysts are described in the Kirk-Othmer Encyclopedia and U.S. Patent No. 407,883, cited above.
2, 3987123, 4086062 and 400
It is described in the specification of No. 8360. For example, the Kirkoosmer Encyclopedia, Volume 12, page 856 describes a complex of hydrochloric acid and aluminum trichloride. The transition metal halide component of the conjugated acid Friedel-Crafts catalyst in this invention is any transition metal halide, especially aluminum.

Consists of halides such as vanadium, boron, titanium, tin, and gallium, and combinations thereof. The halide component can be selected from chloride, bromide, fluoride and iodide. However, iodides are less active in promoting acid-catalyzed organic reactions and are therefore less preferred. The conjugated Friedel-Crafts catalyst of the present invention can be formed from an equimolar amount of sulfuric acid + a heptanoadduct of a transition metal halide, and it is also possible to contain an excess amount of one of these two components. can.

Preferably, the conjugate acid contains from about 0.1 to about 2 moles of transition metal halide per mole of monochalcogen compound-sulfuric acid adduct.

Useful chalcogen compounds - sulfuric acid components are described in U.S. Pat.
Chalcogen compounds can be made by reacting with sulfuric acid according to the method described in No. 45,925. This US patent describes the preparation of a urea-sulfuric acid component free of decomposition products of urea, sulfuric acid, and mono- or di-urea sulfuric acid adducts, which is particularly preferred for the production of the chalcogen compound-sulfuric acid component of the present invention. ing.

As described in U.S. Pat. No. 4,445,925, the reaction of urea and sulfuric acid is highly exothermic and, if not properly controlled, can lead to decomposition of the reactants and products, and the decomposition of sulfamic acid, ammonium sulfamate, ammonium sulfate. This will result in the production of decomposition products such as and other materials. Also, the reaction of sulfuric acid with other chalcogen compounds useful in this invention is exothermic and requires similar precautions, especially in the preparation of highly concentrated solutions and melts.

The formation of such decomposition products and the presence of such decomposition products in the compositions and methods of the present invention are undesirable for several reasons, namely, that the decomposition products interfere with the acid-catalyzed addition of organic compounds or Leaving impurities in the product. Decomposition also results in the loss of active sulfuric acid, which must be combined with useful chalcogen compounds to form active mono-adducts of sulfuric acid.

The solid chalcogen compound-sulfuric acid component useful in the present invention for producing melts and solutions is disclosed in the above-mentioned patent application No. 61
As described for the urea-sulfuric acid component in No. 83264, if there is a surfactant that can be obtained by crystallization from their respective aqueous solutions, the surfactant is heated to approximately the same temperature as the chalcogen compound to the sulfuric acid component. (as described in Japanese Patent Application No. 61-83264) or entrained in a crystallized sulfuric acid adduct. Alternatively, and if desired, a surfactant can be added to the dry or wet crystallized chalcogen compound-sulfuric acid component by any suitable mixing technique.

As stated in the above Japanese Patent Application No. 61-83264,
The aqueous urea-sulfuric acid solution designated as 18-0-0-17 has a crystallization temperature of 10°C. 18-0-0-1
The designation as 7 is commonly used in the agricultural industry to define the weight percentages of nitrogen, phosphorus, potash and a quaternary component, in this case sulfur, included in the composition. That is, 18-0-0-17 contains 18% by weight nitrogen (as urea), 0% by weight phosphorus, 0% by weight potash, and 17% by weight sulfur.

The 18-0-0-17 solution has a urea/sulfuric acid molar ratio of about 1.2 and contains about 90% by weight of a mixture of urea and sulfuric acid. Urea and sulfuric acid in the mixture are approximately 0
．． It constitutes an 80% by weight aqueous solution designated as 10-0-0-19 in the above-mentioned Japanese Patent Application No. 61-83264, having a urea/sulfuric acid molar ratio of 6 and crystallizing at about 6°C. 9
The aqueous solution designated as -0-0-29 consists of a mixture of about 96% by weight urea and sulfuric acid, and about 0.0% by weight.
It has a urea/sulfuric acid molar ratio of 4 and crystallizes at -10°C. The crystallization temperature of the three types of urea-sulfuric acid aqueous solutions mentioned above,
and crystallization temperatures for other formulations of urea and sulfuric acid useful in the compositions and methods of this invention are disclosed in the above-mentioned patent application No. 61-8
3264, shown in part by the isotherms of the ternary phase diagram of urea, sulfuric acid and water.

The crystallization temperatures of other urea-sulfuric acid mixtures and mixtures of sulfuric acid and other chalcogen compounds useful in the compositions and methods of the present invention can be determined from the diagram above or by cooling selected solutions until crystallization occurs. can be determined.

The crystallized material can be separated from the upper aqueous phase by any suitable solid-liquid separation technique, such as filtration centrifugation, thermometry, etc., and optionally the recovered wet solids can be dried by evaporation.

Since a low crystallization temperature is necessary to separate the desired chalcogen compound-sulfuric acid component from the dilute solution, the urea-18-0-0-17 solution containing only about 10% by weight water.
It is preferable to start with a concentrated solution with a high crystallization point, such as a sulfuric acid composition, that is, a solution with a high crystallization temperature, e.g. This is extremely preferable since it requires very little.

Substantially anhydrous solid compositions can be obtained by washing the dry, crystallized chalcogen compound-sulfuric acid component with a strongly hydrophilic solvent such as absolute ethanol or acetone. 100! ! Parts by weight of solvent are suitable for this purpose. A procedure for making a substantially anhydrous urea-sulfuric acid component containing about 1% by weight or less water and which is more thermally stable than aqueous compositions is described in the above-mentioned Japanese Patent Application No. 83264/1988. . This procedure is useful for other thermostable anhydrous chalcogen compounds.
Can be used to make sulfuric acid components.

The anhydrous monoadduct-containing component is stable at ambient conditions and 14
It has negligible pressures up to its decomposition temperature of up to 9°C. However, such components decompose explosively at very low temperatures in the presence of moisture. For example, hydrated urea
The sulfuric acid composition decomposes at 80°C.

The most preferred solid urea composition containing a 1/1 molar urea/sulfuric acid adduct has a melting point of about 37.8°C;
It becomes higher as it deviates in a direction parallel to the isomixer shown in the drawing attached to No.-83264.

The liquid chalcogen compound-sulfuric acid composition used in the method of the invention can be made by any method capable of producing a solution of the desired composition. Therefore, at the time of use, surfactants and/or other ingredients may be added to the concentrated chalcogen compound-sulfuric acid solution during or immediately after manufacture by the process described in U.S. Pat. No. 4,445,925 described above. or such components can be added to the chalcogen compound-sulfuric acid solution prior to its use in catalyzing organic reactions according to the method of the invention.

Alternatively, also at the time of use, the optional ingredients can be mixed with the selected solvent and the solid or concentrated chalcogen compound-sulfuric acid component simultaneously with or afterward. Of course, dissolving the solid chalcogen compound-sulfuric acid composition containing the desired optional ingredients in the selected solvent produces the active liquid composition of the present invention. The melts used in a few examples of the invention can be produced simply by melting the selected solid compositions before or during contact with the organic materials to be converted as described below.

Conjugated Friedel-Crafts acids in the present invention can be made by reacting a chalcogen compound-sulfuric acid component with one or more transition metal halides. This can be done by dissolving in a solvent and dissolving or dispersing the transition metal halide in the product solution. Agitation and elevated temperatures, such as temperatures in the range of about -32°C to about 66°C, increase the rate of formation of the conjugate acid, i.e., the mono-adduct and the transition metal halide mixture.

The reactant-containing composition of the present invention includes 1 or 2 as described below.
One or more organic and inorganic reactants useful in the process of the present invention, including the conjugated Friedel-Crafts catalyst of the present invention.
Alternatively, it can be prepared by mixing two or more chalcogen compound-sulfuric acid components in the presence or absence of an additive solvent or a surfactant. These compositions may be homogeneous solutions or heterogeneous containing liquid-liquid, solid-liquid and gas-liquid mixtures of chalcogen compound-sulfuric acid and/or conjugate acid components and one or more liquid, solid or vapor reactants. Can be made into a mixture.

The novel method of the present invention comprises a catalytically active amount of the chalcogen compound-sulfuric acid component in the presence or absence of additive components such as surfactants, transition metals, halides and/or conjugated Friedel-Crafts catalysts. In the description of the method of the present invention, the chalconigen compound-sulfuric acid component can include a composition containing the above-mentioned additive component. The novel solvent and/or surfactant-containing compositions are preferred for reactions involving relatively compatible organic materials because the surfactant enhances the activity of the chalcogen compound-sulfate compound toward such materials.

Any organic reaction catalyzed by a relatively strong acid, such as sulfuric acid, can be carried out by the method of the present invention.A variety of such reactions are described in the literature, many of which are described in the above-cited Kirkoosmer Encyclopedia. It is stated in
The following acid-catalyzed reactions are shown:
(1) Oxidation such as oxidative addition reactions; (2) Reduction such as reductive addition reactions; (3) Esterification; (4) Transesterification; (5) Hydrogenation; (6) Racemization of optical isomers. isomerization, including C7) alcoholysis and thiolosis (
thiolosis), i.e., hydrolysis, which involves the reaction of organic compounds with alcohols and thiols; (
8) Alkylation; (9) Polymerization of olefinically unsaturated organic compounds 10) Friedel-Crafts reaction; θD demetalization;
and Oz nitration reaction.

Additionally, other reactions known to be catalyzed by acid catalysts can be catalyzed by the chalcogen compound-sulfuric acid components described herein. Certain methods described below can be catalyzed with any of the chalcogen compound-sulfuric acid catalyst components described above, including surfactants and/or transition metal halide-containing components.

Acid-catalyzed oxidative reactions primarily involve the extraction of hydrogen from organic compounds by reacting them with oxidants. An example of this reaction is the oxidative addition of organic compounds as shown in the following reaction scheme: R+H+ RJ + 1'/20x←RIRt + H
2O(1) where R and R2 include straight-chain and side-chain alkanes; alkenes; alkynes; aromatic hydrocarbons; alkyl-, alkenyl- and alkynyl-substituted aryls; and aryl-substituted alkanes, alkenes and alkynes. It refers to the same or different hydrocarbyl groups having any molecular weight and usually having from 1 to about 40 carbon atoms per molecule. Preferred reactants include olefins, especially alpha-olefins.

Acid-catalyzed oxidation reactions can be accelerated by contacting the organic compound to be converted with a catalyst component in the presence of an oxidant, oxygen being the preferred oxidant, as shown in the above formula. The oxidative addition reaction shown in the above formula requires that the organic compound contain a carbon-hydrogen bond capable of undergoing the oxidative addition reaction. The organic compound can be dispersed or dissolved in a melt or solution of the catalyst components in a suitable solvent, or can be contacted with the catalyst components by conventional mixing and contacting means.

The acid-catalyzed reduction reaction of organic compounds in the present invention is as follows:
Includes adding hydrogen to unsaturated organic compounds. Reactions include hydrogenation of organic compounds containing olefins, alkynyl or aromatic unsaturation as shown in the following reaction formula,
and includes reductive addition reactions such as dimerization, oligomerization and polymerization reactions: R, -CH snow CI-Rz+R5-CHIICH-R4+
H! -z R+-Cfb-CH-CI-CHz-R4' and polymer (2) In this formula, R,, R1, R3 and R4 are hydrogen and alkyl mojeties having from 1 to about 20 carbon atoms. ) are the same or different functional groups selected from Preferred reactants include straight and branched chain alkenes and alkenyl aromatics. Acid-catalyzed reduction reactions can contact the organic compound to be converted with hydrogen, a reducing agent such as hydrazine, and/or other reducing agents in the absence of oxidant. This reaction is sufficient to promote a reductive addition reaction in the absence of oxidant of a composition such as a melt, solution or dispersion containing an unsaturated organic compound, a reducing agent and a chalcogen compound-sulfuric acid component. It can be made to produce under conditions of temperature and pressure. The reductive addition of propylene can be facilitated at ambient temperature, as illustrated in the examples below.

Generally, acid-catalyzed esterification reactions according to the method of the present invention convert esterifiable organic compounds having one or more amide, nitrile, carboxylic acid, carboxylic anhydride acyl halides and thiocarboxylic acid groups into organic alcohols or It involves reacting a thiol in the presence of an acid catalyst component. The reaction consists of contacting the chalcogen compound-sulfuric acid catalyst component, one or more esterifiable organic compounds and one or more alcohols, thiols and/or amines under esterification conditions. The reaction of acids, amides, and thioacids can be illustrated by the following reaction scheme: In the above formula, R2 and R2 are any partially hydrolyzed protein or any compound including natural and synthetic polymers such as cellulose, nylon, Dacron, etc. is an organic group, and Y and Z are the same or different divalent groups selected from oxygen, sulfur, and Nl, and χ is any integer of 1 or 2 or more, and An integer in the range of 1000 or more, which affects the molecular weight.For example, partially hydrolyzed polymers such as those described above contain 100 or more functional groups that can withstand esterification by the acid-catalyzed method of the present invention. can contain.

Although not shown in formula (3) above, the reaction of alcohols and thiols with organic cyanides and acyl halides is well known and can be facilitated by the method of the present invention. For example, the reaction of an alcohol with an acyl chloride can be catalyzed by the method of the invention to produce the corresponding ester and hydrogen chloride, and an organic cyanide with water and/or
Alternatively, the reaction of the alcohol produces the corresponding ester and ammonia as described in the above-mentioned Kirkoosmer Encyclopedia, Volume 9, page 302. The generation of ammonia by esterification of nitriles and amides consumes some of the sulfuric acid in the catalyst component, but does not inhibit the occurrence of acid-catalyzed esterification.

The sulfuric acid produced or consumed by ammonia or by other bases present in the esterification reaction (or in other acid-catalyzed reactions encompassed by the process of the invention) may optionally be converted into sulfuric acid during the process. Can be added and substituted to adjust.

Formula (3) above shows that all acyl moieties are related to one organic group designated as R8 and that all alcohol and/or thiol moieties are associated with one organic group designated as R3.
Although shown to be associated with an organic group, this formula is used for illustrative purposes only. For example, a polyfunctional carboxylic acid can be esterified with a large number of monofunctional alcohols; conversely, a large number of monofunctional carboxylic acids, thiol acids, etc. can be esterified with a small number of molecules of polyfunctional alcohols, thiols, etc.

Optional transesterification reactions include (a) ester-ester interchange, (b) alcoholysis, which involves the exchange of alcohol or thiol groups, and (C) interchange of carboxylic acid, thiocarboxylic acid, and/or amide groups. This can be carried out by the method of the invention, which includes acidolysis. Such transesterification reactions involve (1) the chalcogen compound-sulfuric acid component useful in the present invention, (2) the carboxylic ester, thioester and/or amide-ester, and (3) (a) different organic esters, thioesters and/or amides. Ester; (b) Carboxylic acid, thioic acid or amide; (C
) an alcohol and/or a thiol; or (d) by contacting a composition containing a mixture of (a), (b) and (C) above under transesterification conditions. The above reaction can be represented by the following reaction equation: (a) Ester-ester intercrossing t14 (b) Alcoholysis (C) Acidolysis As in the case of transesterification shown in reaction equation (3) above, the reaction The R+, Rz, Rs, and R4 moieties contained in formula (4) are the same or different organic moieties of any molecular weight, and Y and Z are the same or different selected from oxygen, sulfur, and NO groups. It is a divalent group, and X is an arbitrary integer of 1 or 2 or more. In addition, as in the case of transesterification, compounds containing one or more ester groups include monofunctional or polyfunctional esters, alcohols,
Alcohols such as 1-butanol, which can react with thiols, acids, thio acids, etc., can react with simple esters such as ethyl acetate to produce the corresponding butyl esters of amino acids contained in proteins.

The acid-catalyzed hydrogenation reaction in the present invention is (I) R-
organic compounds containing carbon unsaturation, (2) hydrogen and (3)
This can be carried out by contacting a composition containing a chalcogen compound-sulfuric acid-containing catalyst under hydrogenation conditions. The reaction can be carried out by subjecting a composition comprising an acid catalyst component, hydrogen and an unsaturated organic compound to conditions of temperature and pressure sufficient to promote hydrogenation. Hydrogenation of olefin can be shown by the following reaction formula (5).

R+ (CIl=CB)Jg+χHz R+ (CH
t-CHt)
For example, the process of the present invention can be used to hydrogenate ethylene and polymers having molecular weights of too, ooo, or higher, where the polymers contain multiple olefinic bonds. be able to. Also,
The process can be used to hydrogenate benzene, alkyl or alkenyl aromatic hydrocarbons, alkynes and other unsaturated organic compounds. Olefinically unsaturated organic compounds are preferred, especially hydrocarbon compounds having from 2 to about 40 carbon atoms. The hydrogenation reaction can be accelerated with hydrogen, hydrazine or other hydrogenating agents and is preferably carried out in the absence of oxidizing agents such as oxygen and other oxidants.

Acid-catalyzed isomerization reactions include the isomerization of any organic compound having 4 or more carbon atoms;
This isomerization can be carried out by contacting such organic compounds with a useful acid-catalyst component under isomerization conditions. Such an isomerization reaction can be carried out by contacting a composition containing an acid catalyst component and one or more isomerizable organic compounds under isomerization conditions.

Any organic compound can be isomerized by the method of the present invention, including hydrocarbons and organic compounds containing other elements other than carbon and hydrogen, such as oxygen, sulfur, phosphorus, nitrogen, etc. The presence of functional groups in the organic compounds used in the acid-catalyzed isomerization reaction according to the invention, which react in the presence of an acid catalyst component, results in other reactions besides isomerization. Despite this, isomerization occurs.

The isomerization reactions involved in the process of the present invention can be particularly used to isomerize relatively low molecular weight hydrocarbons having from 4 to about 40 carbon atoms per molecule. These reactions can also be used for the racemization of optical isomers, ie, the conversion of dextro- or levorotary-isomers into the corresponding racemic mixtures.

(C
) thiocarboxylic acid esters and polyesters; (d)
Esters and thioethers, including polyoxyethers and thioethers such as cellulose, rayon, starches and other multi-Ws; (e) di- and poly-alkylamines, including polyamines; (f) organics containing olefinic unsaturation. and (6) a reaction that reacts with an epoxide. This hydrolysis reaction involves (1) a chalcogen compound-sulfuric acid component, (2) an amide ester,
acid ester, thioester, ether, thioether,
(3) organic compounds having one or more hydrolyzable functional groups such as amino, olefin and/or epoxy bonds; and (3) hydrolyzable compounds such as water, alcohols, and/or thiols.
ing cos+pound) under conditions of temperature and pressure sufficient to promote hydrolysis of the hydrolyzable functional group. Alternatively, an organic compound having a hydrolyzable functional group such as an amide ester, an acid ester, etc.
The chalcogen compound can be contacted under hydrolytic conditions with a composition containing a sulfuric acid-containing acid catalyst and a hydrolyzable compound.

The uni hydrolysis reaction encompassed by this example of the invention is also encompassed by the transesterification process of the invention including alcoholysis described above. Such reactions involve alcohols and/or thiols with (1) mono- or poly-carboxylic esters or polyesters; (2) -functional or polyfunctional thiocarboxylic esters or polyesters;
and (3) reaction with a mono- or poly-carboxylic acid amide-ester or polyamide ester.

A particularly interesting aspect of the hydrolysis reactions that can be carried out in the process of the present invention is the partial or complete hydrolysis of natural and synthetic polymers such as polysaccharides, proteins, rayon, nylon, etc., including cellulose and starches, etc. This reaction can be carried out by contacting such materials with the acid catalyst component of the present invention containing water. This reaction can proceed at ambient temperature and, if complete, results in complete depolymerization, i.e.
causes complete hydrolysis of the polymer. For example, cellulose can be completely converted to glycols and proteins can be converted to amino acids by this method. Partial hydrolysis of cellulose is carried out using the chalcogen compound used in the method of the present invention.
The remarkable herbicidal activity of the sulfuric acid component can be considered, and the herbicidal activity of the urea-sulfuric acid component is described in the above-mentioned patent application No.
83.264. The ability of surfactants to enhance the activity of the urea-sulfuric acid component and extend control to a variety of plants is also described in Japanese Patent Application No. 61-83.264. Other chalcogen compound-sulfate components exhibit similar herbicidal activity when combined with surfactants.

A portion of the hydrolysis reaction can be illustrated by the following reaction equation, which merely illustrates the acid-catalyzed hydrolysis of Uni encompassed by the method of the present invention: (b) Rt- NH-Rz + R35II RIS
Rl + RJIh Equation (6) above shows the complete acid-catalyzed hydrolysis of amino acid esters, including polyamino acid esters such as proteins, by reaction with a hydrolyzing agent. In Scheme 6(a), R1 can represent any functional organic moiety, Y can represent hydrogen, or a monofunctional terminal organic moiety such as potassium or other metal ion, h is hydrogen, or 1-2 per molecule
represents any organic moiety containing a hydrocarbyl group having 0 carbon atoms, X represents oxygen, sulfur, nitrogen or a combination thereof, and n can represent any integer greater than or equal to 1 . From Reaction Scheme 6(a), when carried out completely, the reaction of protein - monoboly alpha amino acid ester - with water forms the amino acid monomer unit contained in the protein. , R, and R1 illustrate the hydrolysis of dioganoamine by reaction with an organic thiol, which can represent any organic moiety.

Equation 6(C) shows the hydrolysis of an organic thioester by reaction with water to produce the corresponding carboxylic acid and thiol.

As in the case of other hydrolysis reactions encompassed by this example of the invention, the alcohol and/or thiol can be replaced with or combined with water as shown in Scheme 6(C).

Scheme 6 shows the hydrolysis of organic epoxides by acid-catalyzed reaction of the epoxide with water, thiols or alcohols, where R4 and R3 are monovalent moieties selected from hydrogen and any organic moiety. , R6
is a monovalent organic moiety having at least one carbon, and X is selected from oxygen, sulfur and nitrogen.

Hydrolysis of olefins, including polyfunctional olefins, with water, alcohols or thiols can be illustrated by the following reaction scheme: In the above formula, RoRt and R1 are the same or different and are selected from hydrogen and any organic moiety. is a monovalent moiety, X is 0 or S, and n is 1 or 2
Any integer greater than or equal to

The alkylation reaction according to the method of the invention involves the reaction of any organic compound that can be alkylated by an acid-catalyzed reaction with an organic reactant containing olefinic unsaturation.

These reactions can be carried out by contacting an alkylatable organic compound with a composition consisting of a chalcogen compound-sulfuric acid-containing acid catalyst and an olefinic unsaturation-containing organic reactant, and can be represented by the following reaction formula: Possible: R+ + Rz-CH: CH-Rs R+-CH-
C)lx-Rs (8)ffi In the above formula, R2 and R1 are the same or different and represent hydrogen or an organic moiety, in particular an alkyl group having 1 to 10 carbon atoms, and R1 is an alkylatable organic The compounds are, in particular, straight-chain or branched alkanes, aromatic hydrocarbons, alkyl-aromatic hydrocarbons and/or aryl-alkanes having 4 to 20 carbon atoms per molecule.

Acid-catalyzed olefin polymerization reactions involve the polymerization of at least one organic compound having at least one carbon-carbon olefin bond capable of undergoing acid-catalyzed polymerization, in which the organic compound is Contact with a sulfuric acid-containing catalyst in the invention. In this example, the reaction system is preferably substantially free of oxidant. Such a polymerization reaction can be represented by the following reaction formula: where R+ and R1 are hydrogen or a monovalent organic moiety;
It can be selected in particular from hydrocarbyl groups having 1 to 10 carbon atoms, and n indicates the number of monomer units that can be incorporated into the polymer. Copolymers of two or more olefinically unsaturated monomers can be produced. Examples of such copolymers include styrene-butadiene, ethylene-propylene, methacrylic acid-ethyl acrylate-hydroxyethyl acrylate, and ethylene-dicyclopencdiene copolymers, and are also described in Kirkoosmer Encyclopedia, Vol. 12, 852. These include hydrocarbon resins derived from cracked petroleum distillates, turpentine fractions, coal tar fractions and certain olefin monomers, such as the hydrocarbon resins described on pages 1-857.

The Frinibl-Craft reaction involves reacting an organic compound, particularly a hydrocarbon compound capable of undergoing an acid-catalyzed Friedel-Crafts reaction, with a hydrocarbyl halide. This reaction can be effected by contacting one or more organic compounds with a composition consisting of a sulfuric acid-containing catalyst and a hydrocarbyl halide. Such a Friedel-Crafts reaction can be represented by the following reaction equation: R,H+ R,X-+R,R,+Hχ 0ω
In the above formula, R1 is a monovalent organic moiety capable of undergoing a Friedel-Crafts reaction with hydrocarbyl halides, preferably an alkyl group having from 1 to 20 carbon atoms, and X is a halogen, preferably chlorine, Bromine or fluorine, particularly preferably chlorine.

The acid-catalyst component used to catalyze the Friedel-Crafts reaction is the novel conjugated Friedel-Crafts component of the present invention.
It consists of any of the chalcogen compound-sulfuric acid components described above, although acid components containing Friedel-Crafts halide catalysts such as Crafts catalysts are preferred.

Acid-catalyzed demetallation reactions involve the demetalization of organometallic compounds that are capable of undergoing acid-catalyzed demetalization by reaction with water and/or alcohol, and include the organometallic compound, the sulfuric acid-containing catalyst described above. and water and/or alcohol under conditions of time and temperature sufficient to obtain the desired degree of demetalization. This demetallation reaction can be represented by the following reaction formula: (R)J" + aH" -aRH+ M" θl
) In the above formula, R is any organic group including porphyrin and betroborphyriline, M is any metal, and a is the valence of the metal associated with the organic moiety. Also, organic complexes of zero-valent metals can be demetallized by this method. Organo-metallic compounds that can be demetallized by reaction with water and/or alcohol by these methods include, for example, porphyrin,
and betroborphyriline commonly bound to petroleum crudes, tar sands oil, shale oil, coal extracts, etc.

Acid-catalyzed demetalization reactions are carried out in the presence of oxidants such as oxygen, peroxides, ozone, etc., and convert the metals contained in the organometallic compound into a more soluble, higher valence state, if desired. Can be oxidized. Such oxidative demetalization conversion can be performed by contacting a composition containing an organometallic compound, a chalcogen compound-sulfuric acid component, and an oxidant. Similarly, the valence states of metals complexed in metal compounds can be reduced to produce soluble metal ions, for example ferric iron can be converted to ferrous iron. This reaction is an acid-catalyzed demetallation reaction with hydrogen,
It consists of carrying out in the presence of a reducing agent such as hydrazine. This reductive acid-catalyzed demetallation reaction can be carried out by contacting a composition containing an organometallic compound, a chalcogen compound-sulfuric acid component, and a reducing agent.

The acid-catalyzed demetallation reaction in the present invention comprises reacting an organic compound capable of undergoing acid-catalyzed nitration with nitrogen oxides, particularly with nitric acid, to form a nitrating compound (n
It can be carried out by contacting a composition containing nitrogen oxide and a chalcogen compound-sulfuric acid-containing catalyst under nitration conditions. This reaction can be shown by the following reaction formula.

R(H)+s+nNO2(Not)J+nH”
Q7J In this formula, R represents any nitrating organic moiety having a valence of n. Examples of nitration reactions carried out according to the present invention include reactions in which toluene is reacted with nitric acid to produce nitrotoluene and trinitrotoluene (TNT), reactions in which cellulose is nitrated to produce nitrocellulose, and alkanes such as n-decane. There are reactions such as nitration of

The acid-catalyzed organic reactions described above and other known acid-catalyzed reactions combine the organic materials to be reacted with a liquid or solid chalcogen compound-sulfuric acid-containing catalyst and a gas, liquid or solid phase (cellulose, nylon and other (as in the case of solid materials). The liquid catalyst consists of a melt of anhydrous chalcogen compound-sulfuric acid catalyst components, or a solution of such components in an organic feedstock or other solvent. The solid catalyst may consist of a chalcogen compound-sulfuric acid component and the above-mentioned optional components impregnated or ion-exchanged into a solid support, or it may be free of this optional component. Mixed liquid phase reactions can be carried out by forming an emulsion or dispersion of the chalcogen compound-sulfuric acid component melt or solution and the reactants and/or organic materials to be converted.

Novel surfactant-containing chalcogen compound of the present invention
The sulfuric acid component is particularly suitable for acting as an acid catalyst in the conversion of organic materials containing significant amounts of oleaginous materials such as waxes, oils, and high molecular weight organic materials. Such new oil-based materials include, for example, many types of plants (
Mention may be made, for example, of the waxy epidermis of νegetation), proteins, especially fat-containing proteins, ligand-containing cellulosic substances and other oily substances derived from wood and the like.

The acid-catalyzed reaction in the present invention can be carried out at any temperature below the thermal decomposition temperature of the chalcogen compound-sulfuric acid component and above the temperature at which the composition consisting of the chalcogen compound-sulfuric acid component is solidified.

Also, the reaction temperature must be maintained below the temperature at which the organic feed, surfactant, intermediate or product reacts with the chalcogen compound-sulfuric acid component.

The production of any side reaction at any given reaction temperature is
For example, urea-
The reaction temperature used with the sulfuric acid component must be maintained below 80°C, preferably below about 77°C, and in this reaction a significant amount of water is present due to the relatively low decomposition temperature of the urea-sulfuric acid component in the presence of water. exists in Approximately 150°C
Reaction temperatures up to In this case, the urea-sulfuric acid component can be used under anhydrous conditions. However, such high temperatures, i.e., temperatures above 77°C, are preferably avoided unless the reaction system is substantially water-free, i.e., does not contain any detectable amounts of water. Increases as temperature increases. Thermal decomposition temperatures of other hydrous and anhydrous chalcogen compound-sulfuric acid components can be readily determined by gradually increasing the temperature of the selected composition until decomposition results in effervescence or other vapor evolution and discoloration.

The method of the invention can be carried out under any pressure and vacuum as desired. Gas phase reactions, ie, reactions involving organic reactants in the gas phase, can be accelerated by increasing the pressure in the system. Reaction pressures from 0 to 2,000 atmospheres can be used, although pressures from 0 to 100 atmospheres are usually sufficient to achieve acceptable reaction rates.

The acid-catalyzed reaction in this invention contacts twice the organic reactant and the sulfuric acid-containing component in proportion to the desired product yield. In general, as the contact time increases, the conversion increases. Since the reaction rate is influenced by the nature of the reactions involved, the compatibility of the sulfuric acid-containing components with the reactants, the working pressure and temperature, and the reaction time are as desired. Typically, batch contact times of 1 minute to 100 hours are sufficient to achieve complete conversion of most organic materials.
Generally, short reaction times can be used for continuous processes using the method of the invention, where it is desirable to separate unreacted organic materials from the reaction zone effluent and recycle these materials to the reaction zone.

The novel compositions and acid-catalyzed methods of converting organic compounds of the present invention provide compositions and...
Uni has superior advantages over methods. The chalcogen compound-sulfuric acid component is relatively inexpensive, and is also non-corrosive and inexpensive under standard conditions. In addition, such components are highly active protonating agents.
nts), and this makes it possible to perform acid-catalyzed conversions of a wide variety of organic compounds without promoting other acid-catalyzed reactions, especially the side reactions associated with the use of sulfuric acid such as oxidation and sulfonation. It can be used to carry out.

The only particular aspect of the hydrolysis reaction described above is that the polysaccharide is reacted with water in the presence of a chalcogen compound-sulfuric acid composition.
Able to partially or completely hydrolyze multi-vMs ÷
be. This reaction can be carried out to a sufficient degree to produce hydrated polysaccharides such as hydrated sesaccharides, and can be carried out to a sufficient degree to produce hydrated polysaccharides such as hydrated sesaccharides [8 or equivalent monosaccharides]. It can be carried out. The polysaccharides treated in this example and comprising the components of the novel composition include all natural and synthetic virgin polysaccharides having one or more saccharide units per molecule.
in), manufactured and/or chemically pretreated polyP! It includes the class. Therefore, all carbohydrates with one or more sugar units can be hydrolyzed, including oligosaccharides which are usually characterized as polyvMNs with 2 to 8 sugar units per molecule. sugar,
and high molecular weight polysaccharides such as cellulose, rayon, vegetable starch, animal starch (glysigen), and the like.

PolyS1 and mono+sm are made of compounds known as carbohydrates, which are polyhydroxy aldehydes, polyhydroxy ketones, or groups of compounds that can be hydrolyzed to such compounds. As defined, monosaccharides are carbohydrates that cannot be hydrolyzed into simpler compounds. As used for knees, many 11! Class is 2 or 3
Refers to carbohydrates that can be hydrolyzed into 1 or more monosaccharide molecules.

Single I! The groups can contain aldehyde or keto groups, the former being known as aldoses and the latter as kedoses. Hydrolyzable polymeric forms - such as monocellulose - and 'locked' J
Glyose is an extremely abundant aldose. Fructose is a disaccharide. Sucrose (a glutinous ketose that usually combines with glucose).Other common two types include maltose (malt sugar), cellobiose, and lactose (milk protein). Maltose is the main component of starch and can be obtained from starch by partial hydrolysis. Similarly, cellobiose can be derived from cellulose, such as cotton fiber, by partial hydrolysis and can be further hydrolyzed to glucose. .

Lactose; the trisaccharide of glucose and galactose makes up about 5% by weight of milk and is commonly obtained from whey, a by-product of cheese production. Sucrose, generally sugar, is generally obtained from sugar cane and sugar beet, and its constituent single*
- Can be hydrolyzed to glucose and fructose.

Naturally, many poly'IIjM give rise to polymers containing one or more different monosaccharide subunits (although synthetic forms are known), with 100 or 100 monosaccharide subunits per molecule.
It is made from 0 monosaccharide units. Monosaccharide units in polysaccharides and high polysaccharides are linked through glucosidic bonds that can be broken by hydrolysis.

Cellulose, and plant and animal starches are multi-IJ! Often even richer.

Sources of polysaccharides include, for example, wood; paper; crop leaves;
oliage), and stubbles such as cut grass, hay, rice and corn cuttings.
plant material, including wood chips, sawdust, cotton (unprocessed or from clothing waste or other textiles), plant waste;
and plant and animal starches.

The polysaccharide source is not treated or treated with water by one or more chemical or manufacturing processes, such as chemical treatments that remove hydrophobic substances such as lignin or partially hydrate the polysaccharide source. It can be chemically pretreated by a process that is easy to mix. Chalcogen compounds - If not soluble in the sulfuric acid component, such polysaccharide sources are preferably broken up prior to processing; therefore, fine sources such as sawdust, cotton fibers, shredded paper, shredded plant material, etc. Fragment material is an ideal source of polysaccharides. Other large vN-sources, such as wood chips and corn cuttings, can be ground or chopped to increase their surface area prior to processing. A particularly large surface area is preferred for polysaccharide sources containing hydrophobic components, such as lignin, to facilitate contact of useful urea-sulfuric acid hydrolyzers with the polysaccharides; It can be removed by known chemical treatments prior to decomposition.

The relative proportions of chalcogen compound, sulfuric acid, water and polysaccharide can vary significantly depending on the desired rate and extent of hydrolysis.

Since the chalcogen compound-sulfuric acid mixture acts primarily as a catalyst and is not consumed in the hydrolysis reaction (although they are consumed by reacting with impurities), they need to be present in catalytic amounts. However, as the concentration of such a chalcogen compound-sulfuric acid mixture is increased, the reaction rate increases. Therefore, the chalcogen compound and sulfuric acid, in the mixed state, are typically at least about 0.5% by weight, based on the combined weight of the chalcogen compound, sulfuric acid 1, water, and poly-FIs, and at least about 1% by weight per -1G. %, preferably at least about 5% by weight
be present in an amount of Many reaction conditions include chalcogen compound-sulfuric acid concentrations ranging from about 1 to about 90 weight percent, preferably from about 5 to about 50 weight percent, based on total weight.

Water is a reactant and is consumed in the hydrolysis reaction in proportion to the number of moles of water added to the polysaccharide. Hydrolysis of one monosaccharide unit in a polysaccharide molecule to form one free monosaccharide molecule consumes one molecule of water.

Therefore, the concentration of water used in the hydrolysis reaction is sufficient to provide the amount of water required to effect the desired degree of hydrolysis. All of the water can be added initially or in incremental increases during the reaction to replace the water consumed by hydrolysis. To this end, the concentration of water at any given time is at least about 0.1 m-1%, based on the combined weight of chalcogen compounds, sulfuric acid, sphagnum moss, and polysaccharides.
The proportion can be as high as 5% by weight or more. Within this range, the concentration of water can generally be determined by the desired ratio of water to chalcogen compound and sulfuric acid as described above. The concentration of water can also be used to control the rate and extent of hydrolysis, since its presence is necessary for the hydrolysis reaction to proceed. Therefore, an initial water concentration of 1% by weight or less based on poly*i results in 1 part by weight of water being added to the polysaccharide per 100 parts by weight of polysaccharide. High or low initial water concentrations can be used to effect varying degrees of hydrolysis. Additionally, the water concentration can be maintained at a relatively low level;
and the level of water can be replenished in incremental increments or continuously to control the desired rate of hydrolysis.

The polysaccharide can be contacted with the hydrolyzing agent and water described above in the presence or absence of other components by any means capable of achieving the desired contact of each of these components. For this purpose, the chalcogen-sulfate component can be added to an aqueous solution or dispersion of the polysaccharide, or the water-containing chalcogen-sulfate component can be sprayed onto the finely divided polysaccharide-containing material. Alternatively, the multi-vAM feed can also be immersed in a water-containing solution or melt of the acid component, and a light atomization of the polysaccharide-containing feed and the water-containing acid component can be performed.
ng) can be used to effect a small degree of hydration on the surface of multi-SIH.

The reaction must continue for a sufficient period of time to hydrolyze at least a portion of the multi-purpose feed; the reaction time can be increased if complete hydrolysis is required. Therefore, nominal (nomi
nal) short reaction times, relatively low reaction temperatures, low urea-sulfuric acid concentrations, low water concentrations and/or low surfactant concentrations when hydration is required (as in the production of hydrated cellulose). This can be achieved using

However, it is often preferred to hydrolyze at least about 50% of the polysaccharide into its constituent mono[[ and mono I! When the main purpose of the reaction is to produce polysaccharides, almost all, that is, 100%, of the polysaccharides are mono-I! It is preferable to continue the reaction until conversion to Accordingly, reactions usually last for at least 1 minute, generally at least about 5 minutes, and most reactions can be carried out for reaction times of about 5 minutes to about 100 hours. Under mild conditions, for example at an intermediate temperature of 20 to 60°C for about 10 minutes.
A reaction time of about 2 hours is sufficient to completely hydrolyze many polysaccharide sources such as cotton and other plant materials such as rice cuttings, corn cuttings, etc. for example,
400g of cotton contains urea, sulfuric acid and water each in l/1/
It can be completely converted to glycose in 1 hour at 25° C. by soaking in 500 g of a mixture of 1 molar ratio and diluted with 45 g of additional water.

Dilute the reactant-polysaccharide mixture if necessary.
The hydrolysis reaction can be terminated by separating [ from residual reactants and/or by neutralizing the sulfuric acid reactants. Product mixtures containing partially and/or fully hydrolyzed polysaccharides can be used as animal feed or as fermentation medium in the production of fermentation products such as alcohols, or such product mixtures contain monosaccharides and/or partially hydrolyzed polysaccharides. The reaction mixture containing the partially or fully hydrolyzed polysaccharide can be separated to isolate the polysaccharide product for use as animal feed, such as mammals, or to produce alcohol. It can be used as a fermentation medium and other fermentants by known enzymatic and/or bacterial processes. The hydrolysis products are treated with ammonia,
It can be neutralized with a suitable organic or inorganic base such as sodium hydroxide, magnesium hydroxide, etc., some of which act as nutrients to the fermenting bacteria.

Partially hydrolyzed polytIIs that are insufficiently hydrolyzed to dissolve in the reaction medium (such as hydrated cellulose and partially hydrolyzed scum, wood fibers, wood and/or plant materials) are filtered, centrifuged, etc. It can be separated from the reaction medium by conventional physical separation means such as separation, thermometry, and optionally further purified by washing with water or other solvents.

Monotin and/or small molecules soluble in the reaction medium for as much as $1! [can be recovered by such means as crystallization and/or solvent extraction.

Next, the present invention will be explained using examples, but the present invention is not limited thereto.

Han-Tsuchimoto: Hydrolysis of a composite polyether, for example, by completely hydrolyzing cellulose to glycose in the presence of a urea-sulfuric acid component in the present invention will be explained.

Sterile cotton swabs with a urea/sulfuric acid molar ratio of 1.2 and 38.6% by weight of urea, 52.
1% by weight of sulfuric acid and (maintained at a temperature of 21'C) 8
．． 0 dissolved in a urea-sulfuric acid component containing 3% water by weight.
Next, use cotton swabs for about 500 + w j! of the above urea-sulfuric acid components and the mixture was stirred during the operation. Each swab was completely dissolved in approximately 1 minute. The mixture became viscous after the addition of about 20 swabs. An aliquot of the reaction mixture was analyzed by high precision liquid chromatography (lfPLc) to ensure that an amount of glucose corresponding to the stoichiometric conversion of the cellulose feed was obtained for the reaction.

Neither the 11 PLC analysis nor any other observations during the operation confirmed that any reaction other than hydrolysis of cellulose to glucose occurred. No fumes were emitted and the reaction medium did not become colored during the process.

■-Also, this example is a living vegetable.
The use of the urea-sulfuric acid component in the present invention to acid-catalyze the hydrolysis of cellulose and the action of the chalcogen compound-sulfuric acid component as a herbicide in the present invention will be described.

malva (s+alva), cheese weed (che)
ese weed), isbougis (nightsh)
ade), shepherd's purse, penea weed (penea)
pple weed) and the infested first true-leaf stage of purslane.
A 4-kneeker, 4-sided replicate field consisting of onions (approximately 2.54 CI (1 inch)) tall was prepared with a urea/sulfuric acid molar ratio of approximately 1.1 and a urea/sulfuric acid molar ratio of approximately 14.6% by weight. 4701/ha of urea-sulfuric acid component containing urea, 20.8% by weight sulfuric acid and 64.6% by weight water.

The treatment was carried out by applying to the leaves in the amount of In this treatment, within 48 hours after application, all Jffi
M weeds died at a rate of 95-100%, with foliage browning and spots.
The onion crop was not damaged, as assessed by the lack of ttting. The cellulose structure of onion crops was protected by a waxy epidermis, which is typical of young onions. However, such cellulosic structures could also be hydrolyzed by the use of the surfactant-containing chalcogen compound-sulfuric acid component within the scope of the present invention.

(2) Main Example This example shows the hydrolysis of polycarboxylic acid ester and the depolymerization of protein by contact between a chalcogen compound and a sulfuric acid component in the present invention.

Two cosvhide pump seals
pumpseals) with 36.5% by weight of urea, 52.
Contact was made at room temperature for about 70 hours with a urea-sulfuric acid component containing 1% by weight sulfuric acid and 11.4% by weight water and having a urea/sulfuric acid molar ratio of about 1.1. The cowhid seal completely dissolved within 70 hours of contact time.

Two cowhid pump seals were prepared using urea containing 21.5% urea, 55.2% sulfuric acid, and 23.3% water by weight, and having a urea/sulfuric acid molar ratio of approximately 0.6. - The procedure of Example 3 was repeated by contacting with the sulfuric acid component. This composition corresponds to a 10-0-0-18 formulation. The Cowhide pump seal completely dissolved within 70 hours at room temperature.

This example illustrates the oxidative addition of an organic compound and the oxidative addition of propylene in the presence of a chalcogen compound-sulfuric acid component in the present invention. Technical name propylene and air containing 38.6% by weight urea, 52.1% by weight sulfuric acid and 9.3% by weight water, and having a urea/sulfuric acid molar ratio of 1.2. Ingredients approximately 10100O
It was introduced in The urea-sulfuric acid component was housed in a 51,3-hole flask equipped with a stirrer, a feed inlet and an outlet, maintained at 21°C, and a sparger submerged in the urea-sulfuric acid content.
The gas mixture was introduced via. The vapor effluent from the liquid phase was removed from the flask and passed through an ice-cooled liquid trap to collect the reaction product. The liquid phase recovered from the vapor effluent was analyzed by infrared spectroscopy and determined to contain brobylene dimers and higher oligomers of propylene with olefinic unsaturation.

■ Once in the liquid phase created by melting the anhydrous urea-sulfuric acid component containing 42.6% by weight of urea and 57.4% by weight of sulfuric acid and having a urea/sulfuric acid molar ratio of 1.2, a gaseous Propylene and butene were added in mutual reduction by introducing propylene and 2-butene. The liquid phase was maintained at a temperature of 66 °C, and the gas and liquid phases were kept at a temperature of 11
The pressure was maintained at 000 psi (6'9 atm,).

The liquid phase was continuously removed from the reaction zone and flashed to recover vaporizable dimers and polymers of propylene and 2-butene, and copolymers of propylene and 2-butene. High polymers not removed by flushing were extracted from the urea-sulfuric acid melt with n-hexane at a pressure sufficient to maintain the n-hexane in the liquid phase.The recovered urea-sulfuric acid component was recycled to the reaction zone.

A 50-50 molar mixture of emalic acid and glycol containing 36.5% by weight urea, 52.1% by weight sulfuric acid and 1% water at 11.41°C, and 1.1% urea/
A urea-sulfate component with a sulfate mole and a pressure of 1100 psi (
Maleic acid is reacted with 1,2-ethanediol (glycol) by stirring for 10 minutes at a temperature of 60 °C under a pressure of 7,8 atar,
A polyester corresponding to ethanediol was obtained. The produced polymer was extracted from the reaction phase with isopropyl alcohol.

A mixture of benzene, 1-butene and 2-butene was added to 4
At a temperature of 71° C. in the presence of a molten urea-sulfuric acid component containing 2.6% by weight urea and 57.4% by weight sulfuric acid and an alkyl phenol polyethylene oxide surfactant to maintain the reactants in the liquid phase. Benzene was arylated with a mixture of 1-butene and 2-butene to give normal- and iso-butylbenzene by stirring under sufficient reaction pressure. The produced alkylbenzene was recovered by centrifuging the produced reaction phase mixture. Urea-
The sulfuric acid component melt was washed with toluene to complete separation.

Separately - equimolar amounts of 1-chlorobutane and benzene, 42.
Molten urea containing 6% by weight urea and 75.43% sulfuric acid and having a urea/sulfuric acid molar ratio of 1.2
A temperature of 60°C and 1100 psi (7
, 8 atm, ) for 10 minutes to obtain n-butylbenzene. The reaction mixture was cooled to solidify the urea-sulfuric acid component melt, and the product mixture was extracted with toluene to obtain n-butylbenzene. The product was collected. n
The -butylbenzene product was removed from the toluene solvent by solvent distillation and the urea-sulfuric acid component was remelted and recycled to the process.

■-Normal-octane, 42.6% by weight of urea and 5% by weight
Contact with a molten urea-sulfuric acid component containing 7.4% by weight sulfuric acid and having a urea/sulfuric acid molar ratio of 1.2 at a temperature of 71°C and a pressure of 500 psig (35 atm) for 5 minutes. A mixture of isooctane was obtained. The melt was cooled to a temperature of 21 DEG C. to solidify the molten mixture, and the isooctane product was extracted with n-hexane to recover the resulting isooctane mixture. The hexane and isooctane product solutions were separated by distillation and the urea-sulfuric acid was melted and recycled to the reaction zone.

The moon.

petroleum crude oil
containing 36.5% by weight urea, 52.1% by weight sulfuric acid and 11.4% by weight water, and 1.1% by weight of urea/
Aqueous urea to sulfuric acid components having a sulfuric acid molar ratio and a temperature of 71°C and 500 psig (35a
The petroleum crude oil and the urea/sulfuric acid components were contacted and demetalized at a pressure of 100 tm, ) with sufficient stirring to intimately mix the petroleum crude and urea/sulfuric acid components. The resulting petroleum crude with reduced metal content was recovered from the urea-sulfuric acid component by galvanometric flow, washed with water to remove residual urea, sulfuric acid, and metal salts, and dried by distillation.

Flame - ■ Benzene is introduced into a solution of the urea-sulfuric acid component in water containing 15.9% by weight urea and 22.7% sulfuric acid and having a urea/sulfuric acid molar ratio of 1.1. The benzene was nitrated by stirring thoroughly to form a close dispersion of the benzene and urea-sulfuric acid component solutions. Nitric acid is dispersed into a stirred mixture of benzene and urea-sulfuric acid components, and the resulting mixture is heated to a temperature of 66°C and 200 ps.
ig (14.6 atm,). The reaction mixture was cooled and the nitrated benzene product was extracted with toluene to recover the resulting nitrated benzene product.

■ Once 50 g of N-allyl thioformamide was introduced into a 500-flask (immersed in a dry ice bath) with 200-diethyl ether and cooled to 10"C, then 51 g of N-allyl thioformamide previously cooled to 11 °C 98% sulfuric acid was added slowly at a rate slow enough to maintain the temperature of the mixture in the flask below 10 °C, then 200 d of water was added in the flask and the mixture was brought to room temperature (21 °C). sulfuric acid mono-
N-allyl thioformamide adduct was obtained.
A cotton swab was immersed in the mixture at room temperature and maintained for 24 hours to hydrolyze the cotton cellulose.

劃-12 21 g of 98% by weight sulfuric acid and 50 g of 1-(4-aminobenzenesulfonyl)-2-thiourea were mixed as described in Example 13 and the corresponding etc. dissolved in an ether-water mixture were prepared. A molar adduct was obtained.

This adduct can be used to hydrolyze cellulose.

Group - ■ 30 g of 98% by weight sulfuric acid and 50 g of 1-benzoyl urea were mixed as described in Example 13 and ether-
The corresponding equimolar adduct dissolved in a water mixture was obtained. This adduct could be used for cellulose hydrolysis.

■Once 15.5 g of 98% sulfuric acid and 50 g of 1,3-
Bis(2-ethoxyphenyl)carbamide was mixed as described in Example 13 to give the corresponding equimolar adduct dissolved in an ether-water mixture. This adduct could be used for cellulose hydrolysis as described in Example 13.

Group-H The corresponding equimolar adduct of 22 g of 98% by weight sulfuric acid and 50 g of 1-(2-bromo-3-methylbutanoyl)carbamide mixed as described in Example 13 and dissolved in an ether-water mixture. I got it. This adduct could be used for cellulose hydrolysis.

23 g of 98% by weight sulfuric acid and 50 g of ni(4-bromophenyl)carbamide were mixed as described in Example 13 to give the corresponding equimolar adduct dissolved in an ether-water solution. This adduct could be used for cellulose hydrolysis as described in Example 13.

■−■ 34 g of 98% by weight sulfuric acid and 50 g of 1,3-diacetyl carbamide were mixed as described in Example 13 to give the corresponding equimolar adduct dissolved in an ether-water solution. Then propylene and air were mixed. The solution was bubbled through at a temperature of 32° C. and a pressure of 500 psig (35 atm) to obtain propylene dimers and higher oligomers.

- Dish 32.5 g of 98% by weight sulfuric acid and 50 g of 1-ethyl-2-selenourea Example 13
The corresponding equimolar adducts dissolved in ether-water solution were obtained by mixing as described in . Cowhide pump seals were immersed in a solution maintained at 38°C for 24 hours to partially hydrolyze the cowhide proteins.

劃-1, 400g of cotton fiber, 31.3% by weight of urea, 51.1
54 containing wt.% sulfuric acid and 17.6 wt.% water.
5 g of solution and the mixture was stirred at room temperature (about 23° C.) for 1 hour. Urea and sulfuric acid in the mixture constitute 82.4% by weight of the solution and 47.5% by weight of the mixture of polysaccharide (cotton), urea, sulfuric acid and water, and the corresponding proportion of urea and sulfuric acid is l mol urea/sulfuric acid. It was equivalent to the ratio. During the 1 hour reaction time, the cotton "dissolved" to give a colorless syrup. In this case, no significant heat evolution or any gas evolution was observed and the product mixture was titrated with standard base and the final acid concentration was similar to the initial acid concentration. Because of this, no acid consumption occurred. Analysis of the product revealed that it contained glycose and starting urea, sulfuric acid adduct.

Group-U Sawdust 1 from which lignin was removed by liquid ammonia treatment
00 g of the urea-sulfuric acid-aqueous solution described in Example 21 500
The partially hydrolyzed sawdust was partially hydrolyzed by soaking it in 100 g for 2 minutes at 50''C.The partially hydrolyzed sawdust was then separated by filtration and further purified by washing with water.

■-50g of finely ground rice slices (rice 5tubbl)
e) 20% by weight urea, 32% by weight sulfuric acid and 48% by weight
Submerged in 200 g of an aqueous solution containing % water by weight, the product mixture was stirred at 40° C. for 1 hour.

Although the invention has been described above with respect to specific examples,
Various changes can be made to the present invention without departing from the scope of the present specification and claims.

Claims (1)

[Claims] 1. Sulfuric acid; components selected from surfactants, solvents other than water, and combinations thereof; and formulas ▲ Numerical formulas, chemical formulas, tables, etc. ▼ (In the formula, X represents chalcogen, R_1 and R_2
is selected from the group consisting of hydrogen, NR_3R_4 and NR_5, at least one of R_1 and R_2 represents a group other than hydrogen, each of R_3 and R_4 is selected from the group consisting of hydrogen and a monovalent organic group, and R_5 represents a divalent organic group), wherein the molar ratio of the chalcogen-containing compound to the sulfuric acid is about 1/4 to 2 or less. 2. the chalcogen-containing compound and sulfuric acid, in a mixture, account for at least about 1% by weight of the composition;
The composition of claim 1, wherein said chalcogen is selected from the group consisting of oxygen and sulfur. 3. The chalcogen-containing compound and sulfuric acid, in a mixed state, account for at least about 1% by weight of the composition, and the molar ratio is within the range of about 1/1 to 3/2. Compositions as described. 4. a solid mixture of said chalcogen-containing compound, sulfuric acid and a surfactant, wherein said chalcogen-containing compound and sulfuric acid constitute at least about 50% by weight of said composition in the mixture; 2. The composition of claim 1, wherein the composition comprises at least about 0.1% by weight of the compound, and wherein the molar ratio ranges from about 1/2 to about 3/2. 5. an aqueous solution of the chalcogen-containing compound, sulfuric acid and a surfactant, wherein the chalcogen-containing compound and sulfuric acid account for at least about 1% by weight of the composition in a mixture, and the molar ratio is about 1/ 2
2. The composition of claim 1, wherein the composition ranges from about 3/2 to about 3/2. 6. The composition according to claim 1, which does not contain the chalcogen-containing compound and/or a decomposition product of sulfuric acid. 7. The composition of claim 1, wherein the composition is substantially anhydrous. 8. The chalcogen-containing compound and sulfuric acid, in a mixture, account for at least about 80% by weight of the composition, and the molar ratio ranges from about 1/1 to about 3/2; 2. The composition of claim 1, wherein the composition has a melting point of 70[deg.]F. 9. Ingredients selected from the group consisting of surfactants, solvents other than water, and combinations thereof; sulfuric acid and formulas; ▲Mathematical formulas, chemical formulas, tables, etc.▼ (In the formula,
is selected from the group consisting of hydrogen, NR_3R_4 and NR_5, at least one of R_1 and R_2 represents a group other than hydrogen, each of R_3 and R_4 is selected from the group consisting of hydrogen and a monovalent organic group, and R_5 is a divalent organic group) A catalyst composition comprising a monoadduct of a chalcogen-containing compound represented by: 10, (a) Sulfuric acid and formula: ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, X represents chalcogen, R_1 and R_2
is selected from the group consisting of hydrogen, NR_3R_4 and NR_5, at least one of R_1 and R_2 represents a group other than hydrogen, each of R_3 and R_4 is selected from the group consisting of hydrogen and a monovalent organic group, and R_5 represents a divalent organic group) (in which case the molar ratio of the chalcogen-containing compound to the sulfuric acid is about 1/4 to 2 or less); and (b) a surfactant. , solvents other than water, and combinations thereof. 11, Sulfuric acid; Formula: ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, X represents chalcogen, R_1 and R_2
is selected from the group consisting of hydrogen, NR_3R_4 and NR_5, at least one of R_1 and R_2 represents a group other than hydrogen, each of R_3 and R_4 is selected from the group consisting of hydrogen and a monovalent organic group, and R_5 represents a divalent organic group); and an organic compound other than urea that can be catalytically converted by an acid-catalyzed reaction, where the molar ratio of said chalcogen-containing compound to said sulfuric acid is about 1/
4-2 or less. 12. Claim 11, wherein the composition contains an oxidant
Compositions as described in Section. 13. The composition according to claim 11, wherein the composition contains hydrogen and is substantially free of oxidants. 14. The composition of claim 11, wherein said composition comprises a Friedel-Crafts catalyst. 15. The composition according to claim 11, wherein the composition contains a transition metal halide. 16. The composition of claim 11, wherein the organic compound is capable of reacting with and hydrolyzing water in the presence of the mixture of the chalcogen compound and sulfuric acid, and the composition further comprises water. . 17. The composition of claim 11, wherein the organic compound is capable of reacting with an oxidant to oxidize in the presence of the mixture of the chalcogen-containing compound and sulfuric acid, and the composition further comprises an oxidant. thing. 18, the organic compound is capable of chemical reduction by reacting with hydrogen in the presence of the mixture of the chalcogen-containing compound and sulfuric acid, and the composition comprises hydrogen and is substantially free of oxidants; Claim 1
Composition according to item 1. 19. The organic compound is an amino ester, an acid ester,
thioester, ether, thioether, olefin,
comprising chemical bonds selected from the group consisting of epoxy and amino bonds and combinations thereof, which chemical bonds can be hydrolyzed by acid-catalyzed reaction with components selected from the group consisting of water, alcohols, thiols and combinations thereof;
12. The composition of claim 11, wherein the composition further comprises a component selected from the group consisting of water, alcohol, thiol, and combinations thereof. 20. The composition of claim 11, wherein the organic compound has at least one carbon-hydrogen bond capable of undergoing acid-catalyzed oxidative addition, and the composition further comprises an oxidant. 21. The organic compound has at least one carbon-carbon olefin bond capable of undergoing acid-catalyzed reductive addition, and the composition further comprises hydrogen and is substantially free of oxidants. The composition according to item 11. 22. The organic compound comprises a functional group selected from the group consisting of amide, nitrile, carboxylic acid, carboxylic anhydride, acyl halide and thio-carboxylic acid groups and combinations thereof; these functional groups include alcohol, thiol and 12. Acid-catalyzed esterification by reaction with a component selected from the group consisting of combinations thereof, and said composition further comprising a component selected from the group consisting of alcohols, thiols, and combinations thereof. Composition of. 23. The composition of claim 11, wherein said organic compound comprises at least one olefinic bond capable of undergoing acid-catalyzed hydrogenation, and said composition further comprises hydrogen. 24. The organic compound can be alkylated by acid-catalyzed reaction with an organic reactant having olefinic unsaturation, and the composition further comprises a reactant having olefinic unsaturation. Compositions as described in Section. 25. The composition of claim 11, wherein said organic compound comprises at least one carbon-carbon olefin bond capable of undergoing acid-catalyzed polymerization, and said composition is substantially free of oxidants. . 26. The composition of claim 11, wherein the organic compound comprises a hydrocarbon compound capable of undergoing an acid-catalyzed Friedel-Crafts reaction with a hydrocarbyl halide, and the composition further comprises a hydrocarbyl halide. . 27. The composition of claim 11, wherein said organic compound comprises a hydrocarbon having from 4 to about 20 carbon atoms per molecule that is capable of undergoing acid-catalyzed isomerization. 28. said organic compound comprises an organometallic compound capable of undergoing acid-catalyzed demetallation upon reaction with a component selected from the group consisting of water, alcohol and combinations thereof; and said composition further comprises water, alcohol and combinations thereof. 12. A composition according to claim 11, comprising ingredients selected from the group consisting of combinations. 29. The composition of claim 11, wherein said organic compound is capable of undergoing acid-catalyzed nitration by reacting with nitric acid, and said composition further comprises nitric acid. 30. The composition of claim 11, wherein said composition further comprises a component selected from the group consisting of a surfactant, a solvent other than water, and combinations thereof. 31, (a) Catalytic active amount of sulfuric acid and formula: ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, X represents chalcogen, R_1 and R_2
is selected from the group consisting of hydrogen, NR_3R_4 and NR_5, at least one of R_1 and R_2 represents a group other than hydrogen, each of R_3 and R_4 is selected from the group consisting of hydrogen and a monovalent organic group, and R_5 represents a divalent organic group); and (b) an organic compound other than the chalcogen-containing compound that can be catalytically converted by an acid-catalyzed reaction. catalyst composition. 32, transition metal halides, sulfuric acid, and formulas: ▲Mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, X represents chalcogen, R_1 and R_2
is selected from the group consisting of hydrogen, NR_3R_4 and NR_5, at least one of R_1 and R_2 represents a group other than hydrogen, each of R_3 and R_4 is selected from the group consisting of hydrogen and a monovalent organic group, and R_5 1. A catalyst composition comprising a conjugate acid comprising a combination of monoadducts of a chalcogen-containing compound represented by the following formula (indicates a divalent organic group). 33, sulfuric acid, and formulas: ▲Mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, X represents chalcogen, R_1 and R_2
is selected from the group consisting of hydrogen, NR_3R_4 and NR_5, at least one of R_1 and R_1 represents a group other than hydrogen, each of R_3 and R_4 is selected from the group consisting of hydrogen and a monovalent organic group, and R_5 represents a divalent organic group) and an organic compound other than the chalcogen-containing compound and a plant, and the organic compound is an acid-
can be catalytically converted by a catalytic reaction to provide a molar ratio of said chalcogen compound to said sulfuric acid in the composition of about 1/4
A catalyst composition characterized in that it has a molecular weight of 2 or less. 34. Acid-catalyzed reactions of organic compounds with sulfuric acid and formulas: ▲Mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, X represents chalcogen, R_1 and R_2
is selected from the group consisting of hydrogen, NR_3R_4 and NR_5, at least one of R_1 and R_2 represents a group other than hydrogen, each of R_3 and R_4 is selected from the group consisting of hydrogen and a monovalent organic group, and R_5 represents a divalent organic group), said mixture comprising a catalytically active amount of sulfuric acid and a monoadduct of said chalcogen-containing compound. Method of acid-catalyzed reaction. 35. said mixture of sulfuric acid and said chalcogen-containing compound is substantially free of thermal decomposition products of a component selected from the group consisting of sulfuric acid, said chalcogen-containing compound and combinations thereof, and said chalcogen is a compound selected from the group consisting of sulfuric acid and oxygen; 35. The method of claim 34, wherein the method is selected from: 36. The method of claim 34, wherein said reaction is carried out at a temperature below the decomposition temperature of said mixture of sulfuric acid and said chalcogen-containing compound. 37. The method of claim 34, wherein the molar ratio of said chalcogen-containing compound to said sulfuric acid in said mixture ranges from about 1/2 to about 3/2. 38. The reaction is carried out in the presence of an aqueous solution of the chalcogen-containing compound and sulfuric acid, wherein the chalcogen-containing compound and sulfuric acid are present in a mixture at least about 1% of the solution.
35. A method as claimed in claim 34, in weight percent. 39. Claim 34, wherein said reaction consists of oxidation of said organic compound, and said reaction is carried out in the presence of an oxidant.
The method described in section. 40. said reaction consists of catalytic reduction of said organic compound;
and the reaction is carried out in the presence of a reducing agent and in the absence of an oxidant. 41. The method of claim 34, wherein said reaction comprises hydrolysis of said organic compound, and said reaction is carried out in the presence of water. 42. said reaction consists of hydrolysis of said organic compound;
The organic compound comprises chemical bonds selected from the group consisting of amino esters, acid esters, thioesters, ethers, thioethers, olefins, epoxy and amino bonds and combinations thereof; 35. Acid-catalyzed reaction with a component selected from the group consisting of: and wherein said reaction is further carried out in the presence of a component selected from the group consisting of water, alcohols, thiols and combinations thereof. the method of. 43, said reaction comprises an acid-catalyzed oxidative addition of said organic compound, said compound has at least one carbon-hydrogen bond capable of undergoing acid-catalyzed oxidative addition, and said reaction comprises an acid-catalyzed oxidative addition of said organic compound; Claim No. 34 based on the existence of
The method described in section. 44, said reaction comprising the reductive addition of said organic compound, said organic compound having at least one carbon-carbon olefin bond capable of undergoing acid-catalyzed reductive addition, and said reaction further comprising the presence of hydrogen. 35. The method according to claim 34, wherein the method is carried out in the absence of an oxidant. 45. The reaction comprises an acid-catalyzed esterification of the organic compound, wherein the organic compound is selected from the group consisting of amide, nitrile, carboxylic acid, carboxylic anhydride, acyl halide and thio-carboxylic acid groups and combinations thereof. and the reaction consists of an alcohol,
35. The method of claim 34, carried out in the presence of a compound selected from the group consisting of thiols and combinations thereof. 46, said reaction comprising hydrogenation of said organic compound, said compound being capable of undergoing at least one acid-catalyzed hydrogenation.
35. The method of claim 34, wherein the method has at least 1 carbon-carbon olefinic bond, and the reaction is carried out in the presence of hydrogen. 47. said reaction comprises an alkylation of said organic compound, said organic compound being capable of undergoing acid-catalyzed alkylation by reaction with an organic reactant having at least one carbon-carbon olefin bond; and said reaction 35. The method of claim 34, wherein is carried out in the presence of at least one organic reactant having at least one carbon-carbon olefinic bond. 48. A claim in which said reaction consists of polymerization of said organic compound, said compound having at least one carbon-carbon olefinic bond capable of undergoing acid-catalyzed polymerization, and said reaction is carried out in the absence of an oxidant. The method according to item 34. 49, the reaction consists of a Friedel-Crafts reaction of said organic compound, said organic compound being a hydrocarbon capable of undergoing an acid-catalyzed Friedel-Crafts reaction with a hydrocarbyl halide, and said reaction consisting of a Friedel-Crafts reaction of said organic compound in the presence of a hydrocarbyl halide. 35. The method according to claim 34, wherein the method is performed. 50. The method of claim 34, wherein said organic compound is a hydrocarbon having from 4 to about 20 carbon atoms per molecule, and said reaction comprises isomerizing said compound. 51. said organic compound comprises an organometallic compound capable of undergoing acid-catalyzed demetalization by reaction with a component selected from the group consisting of water, alcohols and combinations thereof, and said reaction comprises demetalization of said organometallic 35. The method of claim 34, wherein the method is carried out in the presence of a component selected from the group consisting of water, alcohol and combinations thereof. 52. The method of claim 34, wherein an organic compound is capable of undergoing acid-catalyzed nitration by reaction with nitric acid, and said reaction consists of nitration of said compound and is carried out in the presence of nitric acid. 53. The method according to claim 34, wherein the reaction is carried out in the presence of a transition metal halide. 54. The method of claim 34, wherein said reaction is carried out in the presence of a conjugated Friedel-Crafts acid formed by combination of a monoadduct and a transition metal halide. 55. said reaction is carried out by contacting said organic compound with a composition consisting of said chalcogen-containing compound and sulfuric acid, said chalcogen-containing compound and sulfuric acid representing at least about 80% by weight of said composition in the mixture;
and the molar ratio of said chalcogen-containing compound to said sulfuric acid is in the range of about 1/2 to about 3/2.
The method described in Section 4. 56. The method of claim 34, wherein said reaction is carried out in the presence of a component selected from the group consisting of a surfactant, a polar solvent other than water, and combinations thereof. 57. The method according to claim 34, wherein the mixture of sulfuric acid and the chalcogen-containing compound is supported on a solid support. 58. In a method of carrying out a reaction involving an organic compound that can be acid-catalyzed by sulfuric acid, the reaction is carried out using a catalytically active amount of sulfuric acid and the formula: ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, X represents chalcogen, R_1 and R_2
is selected from the group consisting of hydrogen, NR_3R_4 and NR_5, at least one of R_1 and R_2 represents a group other than hydrogen, each of R_3 and R_4 is selected from the group consisting of hydrogen and a monovalent organic group, and R_5 represents a divalent organic group), and in the mixture the molar ratio of the chalcogen compound to the sulfuric acid is about 1/4.
A method for carrying out a reaction involving an organic compound, characterized in that the reaction temperature is reduced to 2 or less. 59. In the method of showing an acid-catalyzed reaction of an organic compound other than a plant, the reaction is carried out using sulfuric acid and the formula: ▲Mathematical formula, chemical formula, table, etc.▼ (In the formula, X represents chalcogen, R_1 and R_2
is selected from the group consisting of hydrogen, NR_3R_4 and NR_5, at least one of R_1 and R_2 represents a group other than hydrogen, each of R_3 and R_4 is selected from the group consisting of hydrogen and a monovalent organic group, and R_5 represents a divalent organic group), said mixture comprising a catalytically active amount of sulfuric acid and said chalcogen-containing compound. How to react. 60. Polysaccharide, in the presence of water, a catalytically active amount of sulfuric acid and the formula: ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, X represents chalcogen, R_1 and R_2
is selected from the group consisting of hydrogen, NR_3R_4 and NR_5, at least one of R_1 and R_2 represents a group other than hydrogen, each of R_3 and R_4 is selected from the group consisting of hydrogen and a monovalent organic group, and R_5 represents a divalent organic group) under conditions sufficient to at least partially hydrolyze the polysaccharide, and in the mixture, the chalcogen compound is A method for hydrolyzing polysaccharides, characterized in that the molar ratio of the sulfuric acid to the sulfuric acid is about 1/4 to 2 or less. 61. The method according to claim 60, wherein the polysaccharide is a material other than a growing plant. 62. The method of claim 60, wherein the composition comprises a surfactant, a polar solvent other than water, and combinations thereof. 63. The method of claim 60, wherein the polysaccharide comprises cellulose and the method further comprises the step of recovering at least partially hydrolyzed polysaccharide. 64. The polysaccharides can be used on wood, paper, non-livi
61. The method according to claim 60, comprising ingredients selected from ng) plants and combinations thereof. 65. The method of claim 60, wherein the polysaccharide comprises cellulose, and wherein the polysaccharide is contacted with the composition under conditions sufficient to hydrolyze at least a portion of the cellulose to glucose. 66. The method of claim 65, comprising the step of recovering at least a portion of the glucose from the composition. 67. The method of claim 60, wherein the polysaccharide is contacted with the composition under conditions sufficient to hydrolyze at least a portion of the polysaccharide to its constituent monosaccharides.