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Publication numberUS3836525 A
Publication typeGrant
Publication dateSep 17, 1974
Filing dateSep 15, 1970
Priority dateSep 19, 1969
Publication numberUS 3836525 A, US 3836525A, US-A-3836525, US3836525 A, US3836525A
InventorsM Masaki, T Oda, M Uchida, K Yamamoto
Original AssigneeUbe Industries
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Process for the preparation of lactams and sulfonic acid derivatives
US 3836525 A
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Description  (OCR text may contain errors)

United States Patent 3,836,525 PROCESS FOR THE PREPARATION OF LACTAMS AND SULFONIC ACID DERIVATIVES Mitsuo Masaki, Chiba, and Masaru Uchida, Taizi Oda, and Koichi Yamamoto, Ichihara, Japan, assignors to Ube Industries, Ltd., Yamaguchi-ken, Japan No Drawing. Filed Sept. 15, 1970, Ser. No. 72,551 The portion of the term of the patent subsequent to Oct. 24, 1989, has been disclaimed Int. Cl. C07d 41/06 US. Cl. 260-2393 A 3 Claims ABSTRACT OF THE DISCLOSURE A process for the preparation of lactams and sulfonic acid derivatives of active hydrogen-containing organic compounds of the group consisting of oximes, alcohols, phenols, thiols, primary amines and secondary amines, which comprises reacting a lactam-O-sulfonic acid with a compound selected from the specified organic compounds under substantially anhydrous conditions.

This invention relates to a process for the preparation of lactams and sulfonic acid derivatives. More particularly, the invention relates to a process comprising reacting lactim-O-sulfonic acids with active hydrogen-containing organic compounds, thereby producing corresponding lactams and the sulfonic acid derivatives of said organic compounds.

We discovered that when lactim-O-sulfonic acids are treated with active hydrogen-containing compounds selected from the group consisting of oximes, alcohols, phenols, thiols, and primary and secondary amines, the corresponding lactams and sulfonic acid derivatives of the organic compounds are simultaneously obtained.

The lactim-O-sulfonic acids employed in this invention can be represented by the general formula,

in which n is a number of 3 to 11, and each of R and R is hydrogen atom, an alkyl or alkenyl group.

Among such lactim-O-sulfonic acids, those of which R and R are both hydrogen atoms are preferred for the purpose of this invention. Examples of such acid include butyrolactim-O-sulfonic acid, valerolactim-O-sulfonic acid, caprolactim-O-sulfonic acid, enantholactim-O-sulfonic acid, caprylolactim-O-sulfonic acid, pelargonolactim-O- sulfonic acid, caprilactim-O-sulfonic acid, undecanolactim- O-sulfonic acid, and laurolactim-O-sulfonic acid.

Whereas, those lactim-O-sulfonic acids of the formula (I) in which either one or both of R and R are alkyl group, preferably alkyl groups of up to 4 carbons such as methyl, ethyl, and propyl groups; or are alkenyl groups of preferably 2-4 carbons such as vinyl and allyl groups; are also useful for the invention. Examples of such acids include 'y-methylcaprolactim-O-sulfonic acid, v-ethylcaprolactim-O-sulfonic acid, B-propylvalerolactim-O-sulfonic acid, 'y-propylvalerolactim-O-sulfonic acid, 'y-vinylcaprolactim-O-sulfonic acid, 'y-allylcaprolactim-O-sulfonic acid, etc.

As the active hydrogen-containing organic compounds, any of oximes, alcohols, phenols, thiols, and primary and secondary amines can be used in the invention. Upon reacting such an organic compound with lactim-O-sulfonic acid, the compound itself is sulfonated to become a sulfonic acid derivative, While converting the lactim-O-sulfouic acid to the corresponding lactam.

-As the oximes, alicyclic ketoximes of the formula in which n, R and R have the already defined significations, and acyclic ketoximes of the formula NOH in which each of R and R, is a monovalent hydrocarbon radical of up to 14 carbons, for example, alkyl group of up to 10 carbons, cycloalkyl group of 3 to 12 carbons, aryl group of 6-14 carbons, or aralkyl group of 7 to 14 carbons,

are conveniently used.

As the alicyclic ketoximes, those in which the R and R in the formula (II) are hydrogen atoms are particularly preferred, specific examples including cyclobutanone oxime, cyclopentanone oxime, cyclohexanone oxime, cycloheptanone oxime, cyclooctanone oxime, cyclononanone oxime, cyclodecanone oxime, cycloundecanone oxime, and cyclododecanone oxime.

Whereas, those alicyclic ketoximes in which either one or both of R and R are alkyl groups of preferably up to 4 carbons, such as methyl, ethyl, and propyl groups; or alkenyl groups of preferably 2 to 4 carbons such as vinyl and allyl groups, are also useful. Examples of such ketoximes include 4-methylcyclohexanone oxime, 4-ethylcyclohexanone oxime, 3-propylcyclopentanone oxime, 4-vinylcyclohexanone oxime, 4-allylcyclohexanone oxime, etc.

As the examples of acyclic oximes of the general formula (III), acetoxime, methyl ethyl ketoxime, cyclohexyl methyl ketoxime, acetophenone oxime, benzophenone oxime, benzyl methyl ketoxime, etc. may be named.

The alcohols useful in the invention include:

(a) monohydric alcohols of the formula,

R OH (IV) in which R, is an alkyl group of up to 18 carbons, cycloalkyl group of 4 to 12 carbons, or an aralkyl group of 7 to 14 carbons,

for example, methyl alcohol, ethyl alcohol, propyl alcohols, butyl alcohols, amyl alcohols, octyl alcohol, dodecanol, myristyl alcohol, cetyl alcohol, stearyl alcohol, cyclohexanol, methyl cyclohexanol, benzyl alcohol, phenyl ethyl alcohol, cinnamyl alcohol, phenyl propanol, etc.

(b) glycols of the formula,

HOR (OR OH (V) (e) high molecular weight alcohols such as polyvinyl alcohol.

The phenols useful for the invention are those of the formulae,

( ilk in which R, is hydroxyl, an alkyl group of up to 4 carbons,

or nitro group, and k is 0, l, or 2.

and

(VII) R SH (VIII) in which R is an alkyl group of up to 10 carbons, cycloalkyl group of 4 to 12 carbons, aralkyl group of 7 to 14 carbons, or an aryl group of 6 to 14 carbons,

are usable. Specific examples include methylmercaptan,

ethylmercaptan, hexylmercaptan, cyclohexylmercaptan, 4-methylcyclohexylmercaptan, benzylmercaptan, and thiophenol.

As the primary and secondary amines, those of the formula,

are used. Specific examples include primary monoamines such as methylamine, ethylamine, butylamine, cyclohexylamine, benzylamine, phenethylamine, aniline, anisidine, and naphthylamine; secondary monoamines such as dimethylarnine, diethylamine, dibutylarnine, N-methylcyclohexylamine, N-methylbenzylamine, and N-benzylaniline; polyamines such as ethylenediamine, propylenediamine, hexamethylenediamine, phenylenediamine, xylylenediamine, and triethylenetetrarnine; and cyclic: amines such as aziridine, azetidine, pyrrolidine, piperidine, and piperazine.

According to the invention, among those active hydrogen-containing organic compounds, particularly those of the formula,

R YI-I (X) in which Y is oxygen or sulfur atom, or a group, NR

R being hydrogen atom or an alkyl group of up to 6 carbons, and R is a monovalent hydrocarbon radical of 1 to 18 carbons or an alkylideneimino group of the formula,

in which R R and n have the previously defined significations or of the formula,

(XII) in which R and R have the previously defined significations,

when R is an alkylideneimino group, Y being oxygen atom, are preferred.

The reaction of this invention can be illustrated, for example, by the reaction formula below:

(XIII) The reaction of lactim-O-sulfonic acids with active hydrogen-containing organic compounds is performed under substantially anhydrous conditions, preferably in inert, organic solvent. While room temperature is quite satisfactory, the reaction is normally performed at temperatures ranging from -30 C. to 50 C., the lower temperatures being preferred. As the inert, organic solvents, halogenated hydrocarbons such as methylene chloride, ethylene chloride, chloroform and carbon tetrachloride; ethers such as ethyl ether, isopropyl ether, dioxane, and tetrahydrofuran; and aromatic hydrocarbons such as benzene, toluene, xylene, and ethylbenzene; may be named. Obviously, solvents other than above-named may be employed, so far as they are inert, particularly to lactim-O sulfonic acids. The important factor in the reaction is the sufiiciently intimate contact of the lactirn-O-sulfonic acids with the active hydrogen-containing organic compounds. When the reactants are well contacted, the reaction proceeds quantitatively, with ease and at a high rate.

Through the reaction of lactim-O-sulfonic acids with active hydrogen-containing organic compounds, the corresponding lactams and sulfonic acid derivatives of the organic compounds are formed.

The lactams can be represented by the formula,

NH (XIV) in which R R and n have the already defined significations,

and correspond to the lactirn-O-sulfonic acids employed. As such lactams, therefore, butyrolactam, valerolactam, caprolactam, enantholactam, caprylolactam, pelargonolactam, caprilactam, undecanolactam, laurolactarn, other alkyl lactams and vinyl lactams may be named.

According to the invention, together With the above lactams, sulfonic acid derivatives of the employed active hydrogen-containing organic compounds are obtained. For instance, when oximes are used, corresponding oxime- O-sulfonic acids are obtained. Thus, use of alcohols produces alcohol-O-sulfonic acids; that of phenols, phenol- O-sulfonic acids; that of thiols, thiol-S-sulfonic acids; and that of primary or secondary amines, sulfamic acids.

For example, when the oximes of foregoing formulae (II) and (III) are used as the most significant embodiment of the invention, ketoxime-O-sulfonic acids of the formula,

R R (XVI) in which R R R R and n have the previously defined significations are obtained.

Those ketoxime-O-sulfonic acids represented by above general formulae include, for example, acetoxime-O-sulfonic acid, methyl ethyl ketoxime-O-sulfonic acid, cyclohexyl methyl ketoxime-O-sulfonic acid, acetophenone oxime-O-sulfonic acid, benzophenone oxime-O-sulfonic acid, benzyl methyl ketoxime-O-sulfonic acid, cyclobutanone oxime-O-sulfonic acid, cyclopentanone oxime-O-sulfonic acid, cyclohexanone oxime-O-sulfonic acid, cycloheptanone oxime-O-sulfonic acid, cyclooctanone oxime-O- sulfonic acid, cyclononanone oxime-O-sulfonic acid, cyclodecanone oxime-O-sulfonic acid, cycloundecanone oxime-O-acid, and cyclododecanone oxime-O-sulfonic acid.

The reaction products in this embodiment are normally obtained in the form dissolved in the solvent. Therefore, the separation of formed lactam from the ketoxime- O-sulfonic acid is efiected by adding a base to the reaction mixture to precipitate the ketoxime-O-sulfonic acid as a salt with the base, and recovering the lactam from the mother liquor.

As the base useful for this purpose, oxides, hydroxides, carbonates or bicarbonates of alkali metals such as lithium, sodium, and potassium, and of alkaline earth metals such as magnesium, calcium, and barium, etc. may be named, but use of organic bases is more advantageous.

Useful organic bases include:

(1) aliphatic primary amines, such as methylamine, ethylamine, n-butylamine, isobutylamine, ethylenediamine, propylenediamine, and hexamethylenediamine;

(2) aliphatic secondary amines such as dimethylamine,

diethylamine, n-dibutylamine, and diisobutylamine; (3) aliphatic tertiary amines such as trimethylamine, triethylamine, tripropylamine, n-tributylamine, and triamylamine;

(4) alicyclic amines such as cyclohexylamine, N-methylcyclohexylamine, and dicyclohexylamine;

(5) aromatic amines such as aniline, paranitroaniline,

anisidine, N-methylaniline, N,N-diethylaniline, naphthylamine, and N,N-di-n-butylaniline;

(6) nitrogen-containing heterocyclic compounds such as imidazole, pyridine, morpholin, and pyrimidine; and (7) amidines such as benzylthioformamidine and acetoamidine.

The ketoxime-O-sulfonic acids in the reaction mixtures readily form salts, when treated with equivalent quantity of the bases as above-described.

The salts of organic bases with ketoxime-O-sulfonic acids have never been disclosed in prior arts. Since they are stably present in many solvents as precipitates, the above-described separation means is quite valuable as an isolating method of the ketoxime-O-sulfonic acids.

Because the salts of organic bases with ketoxime-O- sulfonic acids form precipitates in the named solvents in majority of cases, they can be easily separated. When the salt is soluble in the solvent employed, the salt can be collected by first removing the solvent and then extracting the formed lactam with a solvent which dissolves the lactam alone.

In the reaction mixtures of the lactams and ketoxime-O- sulfonic acids as obtained in the subject process, it is normally difiicult to cause rearrangement of the ketoxime- O-sulfonic acids to lactim-O-sulfonic acids without additional processing. Whereas, when the halides which are Lewis acids are caused to be present in the reaction mixtures, it is discovered that the ketoxime-O-sulfonic acids can be rearranged to lactim-O-sulfonic acid. In that case, the lactams in the reaction mixtures become complexes of the lactams with the halides.

As the halides which are Lewis acids, those of the general formula,

Mx (XVII) in which M is an element of Group IB of periodic table, such as copper; Group IIB, such as zinc, Group IIIA, such as boron and aluminum; Group IVA, such as tin; Group IVB, such as zirconium; Group VA, such as antimony; or Group VIII, such as nickel and iron;

X is a halogen atom such as fluorine, bromine and chlorine, and

p is a number equalling the valency of M,

are employed. Incidentally, the periodic table referred to herein is that of Werner-Pfeifer. Preferred halides are, by the order of their importance, stannic chloride, stannic bromide, zirconium tetrachloride, zinc chloride, boron trifluoride, antimony pentachloride, boron trichloride, and aluminium trichloride.

The halide may be added to the reaction system after the completion of reaction of the lactim-O-sulfonic acid with the ketoxime, or added in advance of completion of said reaction. Preferably the quantity of said halide is at least stoichiometric to the finally formed quantity of the lactam.

This reaction can be illustrated by the reaction formula below,

(XVIII) in which R R n, M, X, and p have already defined significations, and a is /2 or 1.

The reaction is exothermic, and it proceeds at a suificlent rate at room temperature.

Thus in the presence of a halide which is a Lewis acid in the reaction mixture, the lactam forms a complex with the halide, while the ketoxime-O-sulfonic acid is readily rearranged to lactim-O-sulfonic acid which can be successively used in the reaction with the ketoxime.

According to this embodiment of the invention, it becomes possible to add a large excess of the ketoximes and the halides Which are Lewis acids, to the lactim-O-sulfonic acids present in the reaction system, either incrementally or continuously, recovering substantially all the ketoximes as the complexes of the lactams with the halides.

Because the lactam-halide complexes exhibit less solubility in organic solvents compared with the lactams, they can be recovered as solids from the reaction mixtures. Treating the complexes with bases of stronger basicity than that of the lactams, for example, ammonia, free lactams can be obtained.

When alcohols are used as the active hydrogen-containing organic compound, the products corresponding to the employed alcohols are obtained. For example, methyl alcohol-O-sulfonic acid, ethyl alcohol-O-sulfonic acid, propyl alcohol-O-sulfonic acid, butyl alcohol-O-sulfonic acid, amyl alcohol-O-sulfonic acid, octyl alco'hol-O-sulfonic acid, dodecanol-O-sulfonic acid, benzyl alcohol-O- sulfonic acid, cyclohexanol-O-sulfonic acid, methylcyelohexanol-O-sulfonic acid, ethylene glycol-0,0'-disulfonic acid, propylene glycol-0,0'-disulfonie acid, polyethylene glycol-0,0-disulfonic acid, polypropylene glycol-0,0- disulfonic acid, 1,3-butanediol-0,0'-disulfonic acid, 1,6- hexanediol-0,0'-disulfonic acid, as well as glycerin and polyvinyl alcohol in which the alcoholic residue is sulfonated, are formed.

Similarly, when the phenols of formula (VI) or (VII) are used, phenol-O-sulfonic acids represented by the formulae;

in which R is a radical selected from the group consisting of hydroxyl group, OSO H group, alkyl groups of up to 4 carbons, and nitro group, and

k has the already defined signification,

are formed. Likewise, with the thiols of formula (VIII), thiol-S-sulfonic acids of the formula,

R SSO H in which R has the already defined signfication,

(XXI) are formed, and with the amines of formula (IX), sulfamic acids of the formula,

in which R R 11 and l have the significations as already defined, and R is hydrogen atom or -SO H group, provided at least one of the R s is SO H group.

Example 1 To 90 ml. of ethylene chloride containing 481 mmols of e-caprolactim-O-sulfonic acid, ml. of ethylene chloride containing 3.5 g. of acetoxime (48 mmols) was added dropwise with stirring, at temperatures not higher than 0 C. After the addition the mixture was stirred for 45 minutes at room temperature, and again cooled to 0 C. or below. To the mixture then 50 ml. of ethylene chloride solution containing 3.3 g. (48 mmols) of imidazole was added dropwise. Simultaneously with the addition, color less precipitate was formed. After the addition of imidazole, the stirring was continued for further minutes under cooling. The precipitate was collected by filtration. The yield was 8.9 g. (84%). The melting point of the precipitate was l02-l05 C., and its elementary analysis values were as follows: N: 18.84%, and S: 14.37%, which Well corresponded to the theoretical values of imidazole salt of acetoxime-O-sulfonic acid (C H N O S), which are N: 18.99%, and S: 14.49%.

The filtrate was concentrated under reduced pressure, and from the resulting syrup-like concentrate, 5.3 g. of ecaprolactam was recovered by benzene extraction. The yield was 98%.

Example 2 s-caprolactim-O-sulfonic acid (48 mmols) and 6.5 g. of acetophenone oxime (48 mmols) were allowed to react similarly to Example 1. Then 3.3 g. (48 mmols) of imidazole was added to the reaction mixture. The reaction mixture was concentrated under reduced pressure. The concentrate was dissolved in 10 ml. of ethyl alcohol, and

to the solution ethyl ether was added to form colorless precipitate. The precipitate was collected by filtration. The yield was 6.8 g. (50% The melting point of the product was 92-95 C., and its elementary analysis values were as follows: N: 14.86% and S: 11.08%, which well corresponded to the theoretical values of imidazole salt of acetophenone oxime-Osulfonic acid (C H N O S)which are N: 14.87% and S: 11.32%.

After distilling 01f the solvent from the filtrate by reduced pressure concentration, 3.6 g. of e-caprolactam was recovered from the concentrate by ethyl ether extraction. The yield was 66%.

Example 3 Seventy (70) ml. of ethylene chloride containing 48 mmols of e-caprolactim-O-sulfonic acid was cooled to 0 C., and to which 40 ml. of ethylene chloride containing 4.7 g. (48 mmols) of cyclopentanone oxime was added dropwise with stirring. Thereafter the mixture was slowly heated to room temperature, and then stirred for an hour. The reaction mixture was again cooled to 10 C. or below, and to which a solution of 3.3 g. (48 mmols) of imidazole in 40 ml. of ethylene chloride was added dropwise with stirring. Simultaneously with the addition, generation of heat was observed, and colorless precipitate began to form. The precipitate was collected by filtration. The yield was 7.45 g. (63%). The precipitate had a melting point of 79-84" C., and elementary analysis values of N: 16.90% and S: 12.13%. The values well corresponded to the theoretical values of imidazole salt of cyclopentanone oxime-O-sulfonic acid as C H N O S, which are N: 16.99% and S: 12.97%.

The filtrate was concentrated under reduced pressure, and from the concentrate 5.2 g. of e-caprolactam was recovered by ethyl ether extraction. The yield was 96%.

Example 4 Example 3 was repeated except that the cyclopentanone oxime was replaced by cyclohexanone oxime. Thus 10.0 g; of precipitate was collected. The yield was 80%. The precipitate had a melting point of 114-ll6 C., and elementary analysis values of N: 16.18%, C: 41.54%, and H: 5.78%. The values well corresponded to the theoretical values of imidazole salt of cyclohexanone oxime-O-sulfonic acid as C H N O S, which are N: 16.08%, C: 41.37%, and H: 5.79%.

The filtrate was concentrated under reduced pressure, and from the concentrate 5.1 g. of e-caprolactam was obtained by ethyl ether extraction. The yield was 94%.

Example 5 Seventy (70) ml. ethylene chloride solution containing 48 mmols of e-caprolactim-O-sulfonic acid was cooled to -4 C., and to which a suspension of 9.5 g. (48 mmols) of cyclododecanone oxime in 40 ml. of ethylene chloride was added with stirring. The temperature rose to 30 C. due to the exothermic reaction. The reaction mixture was stirred for 2 hours at room temperature, and cooled to 0 C. T o the mixture then 40 ml. of ethylene chloride solution containing 3.3 g. (40 mmols) of imidazole was added dropwise. Immediately colorless precipitate began to form, which was collected by filtration. The yield was 11.2 g. (68%). The precipitate had a melting point of 157l59 C., and elementary analysis values of N: 12.56% and S: 9.67%. The values well corresponded to the theoretical values of imidazole salt of cyclododecanone oxime-O sulfonic acid as C H N O S, which are N: 12.16% and S: 9.28%.

The filtrate was treated with activated carbon, and concentrated under reduced pressure. To the light yellow concentrate, 30 ml. of water was added to cause precipitation of cyclododecanone oxime. Thus 2.4 g. of the precipitate was collected by filtration (yield: 26% From the filtrate, 5.2 g. of e-caprolactam was recovered by extraction with chloroform. The yield was 96%.

9 Example 6 To a solution of -methyl-e-caprolactim-O-sulfonic acid (48 mmols) in 100 ml. of ethylene chloride, 40 ml. of ethylene chloride solution containing 5.4 g. of cyclohexanone oxime (48 mmols) was added dropwise at 10 C. with stirring. Thereafter the external cooling was stopped, and the reaction mixture was stirred at room temperature. Within approximately 2 hours, the temperature of reaction mixture reached room temperature. The mixture was again cooled to 5 C., then 30 ml. of chloroform solution containing 3.3 g. (48 mmols) of imidazole was added dropwise, and the mixture was stirred for 30 minutes. Then the precipitated crystals were collected by filtration. Thus 9.77 g. of imidazole salt of cyclohexanone oxime-O-sulfonic acid was obtained, which corresponded to 78% of the theoretical yield, i.e., 12.5 g.

The filtrate was concentrated, and the yellowish brown, glutinous residue was homogeneously dissolved in 40 ml. of water. The solution was extracted 5 times with each 30 ml. of chloroform, and the combined extract was dried over anhydrous sodium sulfate, and the solvent was removed. Thus 7.6 g. of brown, glutinous residue was obtained. When the residue was fractionated, 4.9 g. of 'ymethyl-e-caprolactam was obtained as the fraction of distillate at 127130 C./6 mm. Hg. The yield was 90%.

Example 7 To 30 ml. of an ethylene chloride solution containing 24 mmols of laurolactim-O-sulfonic acid, a solution of 2.7 g. (24 mmols) of cyclohexanone oxime in 20 ml. of ethylene chloride was added dropwise at room temperature with stirring. The stirring was continued for further 2 hours at room temperature, after the addition had completed. The reaction mixture was cooled to 0 C., to which a solution of 1.65 g. (24 mmols) of imidazole in 20 ml. of ethylene chloride was added dropwise with stirring. After allowing the mixture to stand overnight at room temperature, the precipitated 0.33 g. of crystalline imidazole sulfate was collected by filtration.

After distilling off a major portion of the ethylene chloride from the filtrate under reduced pressure, 4.0 g. of laurolactam (yield: 85%) was recovered from the residue by benzene extraction. The oily residue (benzene-insoluble component) remaining after the extraction was suspended in 20 ml. of ethylene chloride and stirred. Thus cyclohexanone oxime-O-sulfonic acid-imidazole salt was precipitated. The yield was 4.6 g. (73%).

Example 8 T wenty-four (24) mmols of laurolactim-O-sulfonic acid and 4.75 g. (24 mmols) of cyclododecanone oxime were treated similarly to Example 5, and 1.65 g. (24 mmols) of imidazole was added to the reaction mixture.

Thus precipitated cyclododecanone oxime-O-sulfonic acid-imidazole salt was collected by filtration. The yield was 3.1 g.

The solvent was completely distilled off from the filtrate under reduced pressure, and from the resulting oily residue, 4.4 g. of laurolactam (yield: 93%) was recovered by hot benzene extraction followed by recrystallization from water-methyl alcohol.

The yellow, oily residue remaining after the benzene extraction was dissolved in methyl alcohol, and ethyl ether was added to the solution. Thus precipitated cyclododecanone oxime-O-sulfonic acid-imidazole salt was collected by filtration. The yield was 8.2 g.

The cyclododecanone oxime-O-sulfonic acid-imidazole salt was dissolved in methyl alcohol, and re-precipitated with ethyl ether for purification. The yield was 5.8 g. (70% 10 Example 9 A suspension of 24 mmols of cyclohexanone oxime-O- sulfonic acid in 50 ml. of ethylene chloride was cooled to 0 C., and into which 15 ml. of diethyl ether containing 1.6 g. (27 mmols) of cyclohexylamine was added dropwise with stirring. Simultaneously with the addition, the temperature of the mixture rose by approximately 10 C. due to the exothermic reaction. The suspended cyclohexanone oxime-O-sulfonic acid was once dissolved to form a homogeneous solution, and newly colorless pre cipitate began to form. After the addition, the reaction mixture was gradually warmed up to room temperature, with continuous stirring. After an hours stirring at room temperature, the mixture was concentrated under reduced pressure at 40 C. or below, until the total quantity thereof was reduced to approximately 20 ml. To the residue 50 ml. of diethyl ether was added, and the formed precipitate was collected by filtration. The yield was 6.7 g. The precipitate was washed with diethyl ether, dissolved in methyl alcohol, re-precipitated with diethyl ether, and collected by filtration and dried.

Thus purified precipitate had elementary analysis values as follows: N: 9.29%, and S: 10.70%. The melting point was 156-158 C. The values well corresponded to the theoretical values of cyclohexylamine salt of cyclohexanone oxime-O-sulfonic acid as C H N O S, which are N: 9.58%, and S: 10.96%. The yield was Example 10 Twenty-four (24) mmols of cyclohexanone oxime-O- sulfonic acid and 1.8 g. (25 mmols) of diethylamine were allowed to react and treated similarly to Example 9, and 5.9 g. of precipitate was obtained.

The elementary analysis values of the precipitate were: N: 10.79%, S: 12.03%, C: 45.20%, and H: 8.05%, and the melting point was 136-138 C. The values well corresponded to the caculated values of diethylamine salt of cyclohexanone oxime O sulfonic acid as C H N O S, which are: N: 10.52%, S: 12.04%, C: 45.09%, and H: 8.33 The yield was 92%.

Example 11 A suspension of cyclohexanone oxime-O-sulfonic acid (24 mmols) in 50 ml. of ethylene chloride was cooled to 0 C., to which 15 ml. of ethylene chloride containing 2.5 g: (25 mmols) of triethylamine was added dropwise with stirring. Simultaneously with the addition, the suspended solid was progressively dissolved. After the addition, the reaction mixture was stirred for an hour at room temperature, and thus formed solution was concentrated under reduced pressure to approximately 20 ml. When 50 ml. of diethyl ether was added to the concentrate, colorless precipitate was formed, which was strongly hydroscopic. The yield was 6.15 g. The elementary analysis values of the precipitate were as follows: N: 9.13%, and S: 11.52%. The melting point could not be determined. The analysis values well corresponded to the theoretical values of triethylamine salt of cyclohexanone oxime-O- sulfonic acid as C H N O S, which are N: 9.51% and S: 10.89%. The yield was 87%.

Example 12 Twenty-four (24) mmols of cyclohexanone oxime-O sulfonic acid and 2.0 g. (27 mmols) of tertiary butylamine were treated similarly to Example 9, and 6.32 g. of precipitate was obtained.

The elementary analysis values of the precipitate were: N: 10.14% and S: 11.91%; and its melting point was 163 C. The values well corresponds to the theoretical values of tertiary butylamine salt of cyclohexanone oxime-O-sulfonic acid as C H N O S, which are 'N: 10.52% and S: 12.04%. The yield was 99%.

1 1 Example 13 Twenty-four (24) mmols of cyclohexanone oxime-O- sulfonic acid and 1.6 g. (27 mmols) of isopropylamine were treated similarly to Example 11, and 5.72 g. of precipitate was obtained.

The elementary analysis values of the precipitate were: N: 11.26% and S: 12.98%, and its melting point was 107-1 10 C. The values well corresponded to the theoretical values of isopropylamine salt of cyclohexanone oxime-O-sulfonic acid as C H N O S, which are N: 11.10%, and S: 12.71%. The yield was 94%.

Example 14 Twenty-four (24) mmols of cyclohexanone oxime-O- sulfonic acid and 1.6 g. (27 mmols) of n-propylamine were treated similarly to Example 11, and 5.82 g. of precipitate was obtained.

The elementary analysis values of the precipitate were: N: 10.45%, S: 12.90%, C: 42.87%, and H: 7.84%. The melting point was 125-128 C. The values well corresponded to the theoretical values of n-propylamine salt of cyclohexanone oxime-O-sulfonic acid as C H N O,S, which are N: 11.10%, S: 12.71%, C: 42.84%, and H: 7.99%. The yield was 96% Example 15 A suspension of cyclohexanone oxime-O-sulfonic acid (120 mmols) in 100 ml. of ethylene chloride was cooled to C., to which 11.5 g. (130 mmols) of aniline was added dropwise with stirring. The temperature of the mixture rose to 10 C. due to the exothermic reaction. After 30 minutes stirring, the formed precipitate was collected by filtration, and washed with diethyl ether. The yield was 31.5 g.

The elementary analysis values of the precipitate were as follows: N: 10.01%, C: 50.19%, and H: 6.58%. The melting point was 170-175 C. The values well corresponded to the theoretical values of aniline salt of 'cyclohexanone oxime-O-sulfonic acid as C H N O S, which are N: 9.78%, C: 50.33%, and H: 6.34%. The yield was 92%.

Example 16 To a solution of e-caprolactam-O-sulfonic acid (48 mmols) in 100 ml. of ethylene chloride, a solution of 5.4 g. (48 mmols) of cyclohexanone oxime in 30 ml. of eth ylene chloride was added dropwise at -0 C., with stirring. After the addition the mixture was allowed to gradualy warm up to 18 C., and cooled again to -20 C. Then ml. of ethylene chloride containing 6.24 g. (24 mmols) of stannic chloride was added dropwise to the mixture at said temperature. When the temperature of the reaction mixture was slowly raised, at approximately 10 C. crystalline precipitate began to form. The temperature was further raised to room temperature, and thereafter the mixture was heated to 45 C. for minutes. After adding 10 m. of water to the mixture under cooling, ethylene chloride was distilled off under reduced pressure. Further 40 ml. of water was added to the residue to form a solution. The solution was neutralized with aqueous ammonia under cooling. The gelatinous product was removed by filtration and washed with acetone. The washing and the mother liquor were combined and concentrated to distil off the acetone. The residue was dissolved in 30 ml. of water, and the formed solution was extracted 5 times with each 30 ml. of chloroform. The extract was dried over anhydrous sodium sulfate, and the solvent was removed. Thus 10.0 g. of e-caprolactam was obtained. This result indicates that under the specified reaction conditions, the added cyclohexanone oxime was nearly quantitatively rearranged to caprolactam.

12 Example 17 To a solution of e-caprolactim-O sulfonic asid (48 mmols) in 70 ml. of ethylene chloride, 30 ml. of ethylene chloride containing 5.42 g. (48 mmols) of cyclohexanone oxime was added dropwise at 5 C. or below, with stirring. After the addition, the temperature of the mixture rose gradually, and when it reached 18 C., the mixture was again cooled. At 5 C. or below, 10 ml. of ethylene chloride containing 6.25 g. (24 mmols) of stannic chloride was added dropwise to the mixture. Thereafter the external cooling was stopped, and the mixture was allowed to slowly warm up in the atmosphere of room temperature. The temperature of the reaction mixture reached room temperature after an hour, and further rose due to the exothermic reaction, to as high as 30.0 C. The temperatures above room temperature continued for 2 hours. In the meantime, crystalline precipitate was gradually formed. After 15 hours from the time when the reaction mixture regained room temperature, the precipitate was collected by filtration. Thus 6.10 g. of e-caprolactam-stannic chloride complex was obtained. The yield was 52%.

The filtrate was concentrated, and the residue was dissolved in 40 ml. of water. The solution was neutralized with aqueous ammonia under cooling. The gelatinous product was removed by filtration and washed with acetone. The washing was combined with the former filtrate, and acetone was distilled off therefrom by concentration. The aqueous solution formed by dissolving the residue in 30 ml. of water was extracted 5 times with each 30 ml. of chloroform. The extract was dried over anhydrous sodium sulfate and the solvent was removed. Thus 6.2 g. of e-caprolactam was obtained. The total yield of ecaprolactam was 83%.

Example 18 To a solution of e-caprolactam-O-sulfonic acid (48 mmols) in 70 ml. of ethylene chloride, 30 ml. of ethylene chloride containing 5.42 g. (48 mmols) of cyclohexanone oxirne was added dropwise at 5 C. or below with stirring. Then 10 ml. of ethylene chloride containing 6.25 g. (24 mmols) of stannic chloride was added dropwise. After the addition the external cooling was stopped, and the reaction mixture was left at room temperature. After an hour the temperature of the reaction mixture reached room temperature, and further rose, due to the exothermic reaction, to 30 C. at the highest. The reaction mixture was stirred for 3 hours at room temperature, and cooled again to S C. or below. Whereupon 30 ml. of ethylene chloride solution containing 5.42 g. (48 mmols) of cyclohexanone oxime, and then 10 ml. of ethylene chloride solution containing 6.25 g. (24 mmols) of stannic chloride, were added dropwise to the reaction mixture by the order stated. Then the external cooling was stopped. The temperature of the reaction mixture slowly rose, when it was left at room temperature, to room temperature after 2 hours. The temperature further rose due to the exothermic reaction, to reach 27.5 C. finally. The mixture was allowed to stand for 20 hours at room temperature, and the formed precipitate was collected by filtration. Thus 16.97 g. of e-caprolactam-stannic chloride complex was obtained. The yield was 73%.

The mother liquor separated from the precipitate was concentrated, and the residue was dissolved in water and neutralized with aqueous ammonia under cooling. The gelatinous product was removed by filtration, and washed with acetone. The washing and mother liquor were combined and concentrated. The residue was dissolved in 30 ml. of water, and the solution was extracted 5 times with each 30 ml. of chloroform. The extract was dried over anhydrous sodium sulfate. Recovering the chloroform by distillation, 6.6 g. of e-caprolactam was obtained. The total yield of e-caprolactam was 89%.

13- Example 19 To a solution of .e-caprolactim-O-sulfonic acid (48 mmols) in 80 ml. of ethylene chloride, 30 ml. of ethylene chloride containing 5.4 g. (48 mmols) of cyclohexanone oxime was added dropwise at 12-4.5 C. with stirring. The resulting solution was first heated to C., cooled again to 10" C., and to which 25 ml. of ethylene chloride containing 7.17 g. (24 mmols) of antimony pentachloride was added dropwise. The addition completed within minutes. The temperature of the mixture then was -4 C. The external cooling was stopped, and the mixture was stirred at room temperature. The temperature of the mixture reached room temperature within an hour. The stirring was further continued for additional 3 hours, and then the reaction mixture was neutralized with aqueous ammonia under cooling. Thus formed precipitate was removed by filtration, and washed with water. The filtrate and the washing were combined, and extracted 5 times with each 50 ml. of chloroform.

The extract was dried over anhydrous sodium sulfate, and chloroform was removed. Thus 9.1 g. of e-caprolactam was obtained, which corresponded to 84% of the theoretical .e-caprolactam yield, i.e., 10.8 g., under the assumption that the added cyclohexanone oxime were completely rearranged.

Example To a solution of ecaprolactim-O-sulfonic acid (48 mmols) in 70 m1. of ethylene chloride, 20 ml. of ethylene chloride containing 5.4 g. (48 mmols) of cyclohexanone oxime was added dropwise at 11 C. to 5" C. with stirring. To the mixture then 20 ml. of ethylene chloride containing 6.92 g. of boron trifluoride-ethyl ether complex was added dropwise at 10 C. The addition completed 7 minutes. The temperature of the reaction mixture then was 7 C. The external cooling was stopped, and the mixture was continuously stirred at room temperature. The temperature of the mixture reached room temperature after 40 minutes. After additional 4 hours stirring at room temperature, ml. of water was added to the mixture. Distilling ethylene chloride off from the mixture under reduced pressure the aqueous phase was extracted 5 times with each 50 ml. of chloroform. The extract was dried over anhydrous sodium sulfate, and from which the solvent was recovered. Thus 9.9 g. of e-caprolactam containing cyclohexanone and oxime thereof was obtained. The e-caprolactam content was 7.15 g., which corresponded to 66% of the theoretical e-caprolactam yield, i.e., 10.8 g., under the assumption that all the cyclohexanone oxime added were rearranged.

Examples 21-3 6 In these Examples, lactim-O-sulfonic acids were allowed to react with alcohols by one of the following four methods, and the formed lactams and alcohol-O-sulfonic acids were separately recovered.

[Method A] To 80 ml. of ethylene chloride containing 48 mmols of lactim-O-sulfonic acid, 10 ml. of ethylene chloride containing 48 mmols of alcohol was added dropwise with stirring at room temperature. The mixture was then stirred at room temperature for 30 minutes, heated to 50 C., and further stirred for 30 minutes at 50 C. The reaction mixture was concentrated under reduced pressure, to allow recovery of the ethylene chloride.

The syrup-like concentrate was dissolved in 50 ml. of ice water, and the solution was neutralized with lON aqueous caustic soda. The solution was then extracted 5 times with each 20 ml. of chloroform. The extract was dried over anhydrous sodium sulfate, from which chloroform was expelled to leave free lactam.

The aqueous solution remaining after chloroform extraction was concentrated under reduced pressure, and

14 20 ml. of ethyl alcohol was added to the concentrate. Allowing the mixture to stand, precipitated crystalline sodium alcohol-O-sulfonate was collected by filtration.

[Method B] To ml. of ethylene chloride containing 48 mmols of lactirn-O-sulfonic acid, 10 ml. of ethylene chloride containing 48 mmols of alcohol was added dropwise at room temperature vw'th stirring. The mixture was thereafter stirred for an hour at room temperature, heated to 50 C., and further stirred for an hour at 50 C. The reaction mixture was concentrated under reduced pressure to allow recovery of ethylene chloride.

The syrup-like concentrate was dissolved in 30 ml. of water, and neutralized with sodium bicarbonate. The aqueous solution was then extracted 5 times with each 20 ml. of chloroform, and the extract was dried over anhydrous sodium sulfate. Thus removing chloroform therefrom, lactam was obtained.

The aqueous solution remaining after the chloroform extraction was treated with activated carbon. Then 100 ml. of an aqueous solution containing 48 mmols of S-benzylthioformamidine hydrochloride was added to the aqueous solution. In case no precipitate was formed in the above procedure, the resultant solution was further concentrated under reduced pressure and ethyl alcohol was added to the concentrate. Thus formed crystalline precipitate of alcohol-O-sulfonic acid S-benzylthioformamidine salt was collected by filtration.

[Method C] To 80 ml. of ethylene chloride containing 48 mmols of lactim-O-sulfonic acid, 20 ml. of ethylene chloride containing 24 mmols of alcohol was added dropwise at room temperature with stirring. Thereafter the mixture was stirred for 30 minutes at room temperature, heated to 50 C., and further stirred for 30 minutes at 50 C. The reaction mixture was concentrated under reduced pressure, to allow recovery of ethylene chloride.

The syrup-like concentrate was dissolved in 20 ml. of water, and neutralized with aqueous barium hydroxide. The aqueous solution was extracted 5 times with each 20 ml. of chloroform. The extract was dried over anhydrous sodium sulfate, and chloroform was expelled therefrom to leave free lactam.

The aqueous solution remaining after the chloroform extraction was treated with activated carbon, and concentrated under reduced pressure to approximately 5 ml. Ethyl alcohol was added to the concentrate to cause precipitation of barium alcohol-0,0-disulfonate dihydrate, which was collected by filtration.

[Method D] To ml. of ethylene chloride containing 48 mmols of lactim-O-sulfonic acid, 20 ml. of ethylene chloride containing 48 mmols of alcohol was added dropwise at 10 C. or below with stirring. Then the mixture was allowed to stand for 12 hours at room temperature. The reaction mixture was concentrated under reduced pressure to allow recovery of ethylene chloride.

Upon addition of 50 ml. of water to the syrup-like concentrate, lactam was precipitated. The aqueous solution was neutralized with sodium bicarbonate, and the lactam was collected by filtration.

The filtrate was concentrated under reduced pressure, and to the concentrate ethyl alcohol was added to cause precipitation of sodium alcohol-O-sulfonate monohydrate, which was collected by filtration.

The results of Examples 21 through 36 are collectively given in the following table, in which BTFA stands for S-benzylthioformamidine,

rose gradually to 13 C. Then again the mixture was cooled to 30 C., to which imidazole (3.3 g., 48 mmols) was added with stirring. Immediately colorless crystals were precipitated. After two hours stirring at room temperature, 6.0 g. of the colorless crystals were collected by filtration, which was identified with thiophenol-S-sulfonic acid-imidazole salt (m.p. 1015-1035 C.) synthesized by known method, by IR spectrum. The mother liquor from which the crystals had been filtered off was concentrated under reduced pressure to allow distillation off of ethylene chloride. The residue was dissolved in 30 ml. of water, and neutralized with aqueous ammonia. The aqueous solution was extracted with benzene (30 ml. 2). The aqueous phase separated from the benzene phase was extracted with chloroform (40 ml. From the chloroform extract, 4.95 g. (91%) of e-caprolactam was obtained.

Example 39 To a solution of e-caprolactim-O-sulfonic acid (48 mmols) in ethylene chloride (70 ml.), another solution of cyclohexylarnine (9.5 g., 96 mmols) in ethylene chloride (30 ml.) was added dropwise at room temperature, with stirring. The addition required minutes, and at the end thereof the temperature of the reaction mixture reached 37 C. The mixture was further stirred for 5 hours at room temperature, and filtered. Thus 3.67 g. of colorless crystals were collected, which was confirmed to be N- cyclohexylsulfamic acid cyclohexylammonium salt containing a minor amount of cyclohexylamine sulfate, by means of infrared absorption spectrum. The crystals were treated with 30 ml. of water, and whereupon 0.63 g. of pure N-cyclohexylsulfamic acid cyclohexylammonium salt was obtained.

The ethylene chloride solution separated from the above crystalline mixture by filtration was concentrated under reduced pressure. The residue was dissolved in water, and the aqueous solution was rendered acidic with 1N hydrochloric acid, and extracted 4 times with each each 50 ml. of chloroform. All the extracts were combined, and from which chloroform was removed. The residue was again dissolved in water, and made basic with 1N caustic soda. The aqueous solution was extracted 5 times with each 50 ml. of chloroform. The extract was dried over anhydrous sodium sulfate and the solvent was removed. Thus 4.1 g. (76%) of e-caprolactam was obtained.

Example 40 To a solution of e-caprolactim-O-sulfonic acid (48 mmols) in ethylene chloride (80 ml.), another solution of benzylamine (10.3 g., 96 mmols) in ethylene chloride ml.) was added dropwise at room temperature with stirring. The addition required 20 minutes. In the meantime, the temperature of the reaction mixture reached at the highest 40 C., and crystals were precipitated. The reaction mixture was heated under reflux for 3 hours and cooled. The crystalline precipitate was collected by filtration. Thus 7.2 g. of N-benzylsulfamic acid benzylammonium salt was obtained, which was identified with the named salt as its infrared absorption spectrum was iden tical with that of the named compound synthesized by known means. The yield was 51%. The mother liquor separated from the sulfamic acid salt by filtration was concentrated under reduced pressure, and the residue was dissolved in water. The aqueous solution was rendered acidic with 0.1 N hydrochloric acid, and extracted 5 times with each 50 ml. of chloroform. The extract was dried over anhydrous sodium sulfate, and chloroform was recovered therefrom. Thus 2.9 g. (54%) of e-caprolactam was obtained.

Example 41 To a solution of e-caprolactim-o-sulfonic acid (48 mmols) in ethylene chloride (80 ml.), another solution of aniline (8.93 g., 96 mmols) in ethylene chloride (20 ml.) was added dropwise at --5 C. or below with stirring. After the addition the stirring was continued for 30 minutes, and thereafter the reaction mixture was heated under reflux for an hour. The mixture was allowed to stand in the atmosphere of room temperature and to cool off, and the precipitated crystals were collected by filtration. Thus 11.1 g. of phenylsulfamic acid anilinium salt was obtained. The yield was 87%.

The mother liquor separated from the crystals was concentrated under reduced pressure. Then the aqueous solution formed by adding 50 ml. of water to the residue was extracted with 50 m1. of diethyl ether. The aqueous phase separated from the ether phase was extracted 5 times with each 50 ml. of chloroform. From the chloroform extract, 5.0 g., of e-caprolactam was obtained. The yield of the e-caprolactam was 93% What is claimed is:

1. A process for the preparation of lactams and sulfonic acid derivatives of active hydrogen-containing organic compounds which comprises reacting at a temperature of 30 to 50 C. a lactim-O-sulfonic acid of the formula C-OSOaH l 2)n N wherein n is a number of 3 to 11, and R and R are each a hydrogen atom, an alkyl group of up to 4 carbon atoms or alkenyl group of 2 to 4 carbon atoms, with an active hydrogen-containing compound selected from the group consisting of (i) alicyclic ketoximes of the formula wherein 11, R and R are as defined above; (ii) acyclic ketoximes of the formula wherein R and R are each an alkyl group of up to 10 carbon atoms, cycloalkyl group of 3 to 12 carbon atoms, aryl group of 6 to 14 carbon atoms, or aralkyl group of 7 to 14 carbon atoms; (iii) monohydric alcohols of the formula wherein R is an alkyl group of up to 18 carbon atoms, cycloalkyl group of 4 to 12 carbon atoms, or aralkyl group of 7 to 14 carbon atoms;

(iv) glycols of the formula wherein R is an alkylene group of 2 to 8 carbon atoms, or xylylene group, and m is zero or an integer of 1 to 3;

(v) polyhydric alcohols selected from the group consisting of glycerine, 1,2,6-hexanetriol, 1,1,1- trihydroxymethylpropane, pentaerythritol and polyvinyl alcohol;

(vi) phenols of the formulae and (R1)k wherein R is a hydroxyl group, an alkyl group of up to 4 carbon atoms or nitro group, and k is 0, 1, or 2;

(vii) thiols of the formula wherein R is an alkyl group of up to carbon atoms, cycloalkyl group of 4 to 12 carbon atoms, aralkyl group of 7 to 14 carbon atoms, or an aryl group of 6 to 14 carbon atoms; and

(viii) primary and secondary amines of the formula,

under substantially anhydrous conditions.

2. A process for the preparation of lactams and ketoxime-O-sulfonic acids, which comprises reacting a lactim- O-sulfonic acid of the formula wherein n is a number of 3 to 11, and R and R are each a hydrogen atom, an alkyl group of up to 4 carbon atoms or alkenyl group of 2 to 4 carbon atoms, with a ketoxime selected from the group consisting of (i) alicyclic ketoximes of the formula wherein in, R and R are as defined above; and (ii) acyclic ketoximes of the formula NOH wherein R and R are each on alkyl group of up to 10 carbon atoms, cycloalkyl group of 3 to 12 carbon atoms, aryl group of 6 to 14 carbon atoms, or aralkyl group of 7 to 14 carbon atoms,

under substantially anhydrous conditions and in an inert organic solvent, at a temperature within the range of from 30 C. to 50 (3.; adding to the resulting reaction mixture an organic base selected from the group consisting of aliphatic amines, alicyclic amines, aromatic amines, nitrogen-containing heterocyclic compounds and amidines; recovering the ketoxime-O-sulfonic acid in the form of a salt of said organic base, as a solid; and recovering said lactam from the formed mother liquor.

3. A process for the preparation of lactams, which comprises reacting a lactim-O-sulfonic acid of the formula COSOaH Rim). ll N wherein n is a number of 3 to 11, and R and R are each a hydrogen atom, an alkyl group of up to 4 carbon atoms or alkenyl group of 2 to 4 carbon atoms, with an alicyclic ketoxime of the formula wherein 12, R and R are as defined above, under substantially anhydrous conditions, in an inert organic solvent, at a temperature within the range of from 30 C. to C.; and subsequent to the reaction adding to the reaction system a halide of the formula MX wherein M is an element of Group B, HB, IIA, IVA,

IVB, VA, or VIII of the Periodic Table, X is a halogen atom, and p is a number equal to the valency of M,

thereby converting the formed lactam to a complex with said halide while rearranging the formed alicyclic ketoxime-O-sulfonic acid to a lactim-O-sulfonic acid.

References Cited UNITED STATES PATENTS 3,119,814 1/1964 Bigot et al 260239.3 A 3,687,938 8/1972 Masaki et al 260239.3 A

HENRY R. JILES, Primary Examiner R. T. BOND, Assistant Examiner US. Cl. X.R.

260-2393 R, 326.82, 326.5 FN, 326.5 FL, 293.86, 566 A, 553 R, 513.6, 451, 456, 239 B, 293.85

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. ,836,525 Dated September 17, 1974 Inventor-(s) Mitsuo MASAKI ET AL It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

In the Heading, insert 'patentees' Foreign Application Data as follows:

-- Japanese Application No. 44 7399O/69, filed Sept. 19, 1969 Japanese Application No. 44-73991/69, fjiled Sept. 19, 1969 In Claim 1, last formula inv column 18': cancel "R -OH" and substitute therefor RS-SH Signed and sealed this 3rd day of. December 1974.

(SEAL) Attest: I

M. GIBSGN JR. C. MARSl IALL DANN ggiting Officer Commissioner of Patents F ORM PO-l 050 (10-69) USCOMM-DC 60376-969 v 11.5. GOVERNMENT Pmm'mc OFFICE: @959 o-ass-n-a

Referenced by
Citing PatentFiling datePublication dateApplicantTitle
US3884953 *Jun 19, 1974May 20, 1975American Cyanamid Co1-Alkoximino-2-({107 -substituted-alkyl)-2-cyclopentenes
US4094896 *Dec 2, 1976Jun 13, 1978American Cyanamid Company1-Alkoximino-2-(ω-substituted-alkyl)-2-cyclopentenes
US5571913 *Aug 19, 1994Nov 5, 1996Dsm N.V.Rearrangement of alicyclic ketoxime in the presence of lactim-o-sulfonic acid in the presence of acid cation exchanger
EP0639565A1 *Aug 17, 1994Feb 22, 1995Dsm N.V.Process for preparing a lactam
Classifications
U.S. Classification540/464, 548/543, 558/4, 548/552, 540/535, 546/243, 558/20
International ClassificationC07B45/02, C07D201/02, C07C303/32, C07D201/14
Cooperative ClassificationC07B45/02, C07D201/02, C07C303/32, C07D201/14
European ClassificationC07B45/02, C07C303/32, C07D201/14, C07D201/02