DE1228604B - Process for the production of alpha-chloroximes - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

GERMAN

PATENT OFFICE

EDITORIAL

Int. Cl .:

C07c

German class: 12 ο-22

Number: 1228 604

File number: S 83570IV b / 12 ο

Filing date: February 2, 1963

Opening day: November 17, 1966

The present invention relates to a process for the preparation of -chloroximes and their Sulphates, in particular, refer to a method to directly produce compounds that have an olefinic double bond contain, a-chloraldoxime and «-chlorketoxime and to obtain their corresponding sulfates.

It is known that α-chloroximes in general be obtained in such a way that a-chlorocarbonyl compounds, in particular -chloraldehydes and α-chloroketones with hydroxylamine and its salts lets react. However, this process has the disadvantage that it is very difficult to obtain the α-chloroximes in the pure state from the reaction mixture to win.

It is also known that -chloroximes are formed by the addition of nitrosyl chloride to olefins can, however, several by-products are formed.

An improved proposal was the use of nitrosyl chloride in the presence anhydrous hydrochloric acid recommended, but even in this case the yields are not always satisfactory, and the reaction products are always with by-products, e.g. B. dimeric chloronitroso compounds, contaminated.

The above-mentioned process also requires the use of nitrosyl chloride, which is known at Room temperature is a gaseous product and is therefore difficult to handle.

The present invention is a process for the preparation of -chloroximes with better yields than have been achieved with the previously known processes.

The process is characterized by its simple execution and ensures the production of Λ-chloroximes with high purity, using of cheap and abundant raw materials as starting material.

The present invention also relates to a process for the preparation of sulfates of the corresponding «-Chloroxime, especially the sulfate of a-chlorocyclohexanone oxime, which is an important Intermediate product for numerous organic syntheses, especially for the production of «-chlorocyclohexanoxime is.

Numerous are the advantages of the method of the present invention compared to those heretofore described process to obtain α-chloroxime, z. B. higher yields, use of a nitrosating agent, easier handling, none special requirements in terms of temperature and pressure. Process for the production of α-chloroximes

Applicant:

Societä Edison, Milan (Italy)

Representative:

Dr.-Ing. H. Negendank, patent attorney,

Hamburg 36, Neuer Wall 41

Named as the inventor:

Adriano Nenz,

Corrado Brichta,

Giuseppe Ribaldone,

Giampiero Borsetti, Milan (Italy)

Claimed priority:

Italy of February 3, 1962 (2137),

dated September 20, 1962 (27,343)

and reaction conditions; Ease of separating the desired reaction products. The process according to the invention for the preparation of -chloroximes by reacting a nitrosyl compound in the presence of anhydrous hydrogen chloride with an olefin of the general formula

R ₁ .
R. '

: c = c:

-R ₃ H

wherein R ₁ , R ₂ and R _{3 are} hydrogen atoms, alkyls, cycloalkyls, aralkyls or aryls, or R ₁ and R ₂ or R ₁ and R _{3 are} a common cycloaliphatic ring with 4 to 12 C closed by a CH _{2 group} -atoms form, is characterized in that the olefin at a temperature between about -30 and about + 3O ⁰ C, preferably at 0 ° C, is reacted with nitrosyl sulfuric acid and from the obtained ot-Chloroximsulfat the "-Chloroxim optionally by the addition of Releases water. According to the present invention, α-chloroximes are obtained by allowing nitrosylsulfuric acid to react with organic compounds in the presence of anhydrous hydrochloric acid

609 727/436

3 4

contain an olefinic double bond and little after dilution of the corresponding sulfates with

at least 1 hydrogen atom on one of the double water, by means of decantation, filtration, extraction

bond belonging to the carbon atoms. separated or recovered with solvents.

Inert solution can also be used in the reaction. The process according to the present invention

use medium. The oc-chlorooximes formed can be schematized as follows:

R _:

J ^ C = CC '+ NOHSO ₄ + HCl > ^ C -C · H ₈ SO ₄

R ₈ HR ₂ II

Cl NOH

where R ₁ , R ₂ and R _{3 have} the meaning given above a-chloroxime sulfate both soluble and insoluble in

to have. Above solvents can be.

Examples of the as ^ starting material to be used As a solvent for the olefins, being at the same time

The following olefins are used: Ethylene, propylene, oligomers that are soluble in α-chloroxime sulfate, come as follows

des propylene, butene- (1), butene- (2), isobutene, pentene, ao in question: acetic acid, propionic acid, nitrobenzene,

Hexene, heptene, etc., cyclopentene, cyclohexene, methylene chloride, liquid sulfur dioxide, etc.

Methylenecyclohexane, limonene, methylcyclohexene, the solvents for olefins, in which the a-chlorine-

Cyclododecene, styrene, cyclooctene, etc. oxime sulfate is insoluble are: aliphatic and

When using cyclohexane, this cycloaliphatic hydrocarbon compound, such as olefin mixed with cyclohexane for the reaction, can be transferred to hexane, cyclohexane, or the olefin itself. Such technical cycloolefin, aromatic hydrocarbon compounds, cycloparaffin mixtures are, according to a new method, such as benzene or toluene, some chlorinated hydrocarbons according to Italian patent 665 335 are compounds such as carbon tetrachloride,
in the name of the same inventor easily and in tech- Although the process can also be prepared from cyclohexane in the absence of a small scale, where solvents can be carried out, it is preferred to use solvents by a method of preparation that is easy to carry out, because this is easier to obtain oc- Chlorocyclohexanone oxime allow thermal control of the reaction and using cyclohexane as the starting material ensures a more regular course of the same.

To carry out the process according to the present invention, the reaction temperature can vary widely

the invention is generally proceeded so that limits vary; good results are achieved in the

that in the reaction vessel the olefins without a temperature range between -30 and +30 ⁰ C and

or diluted with a solvent with the preferably at about O ⁰ C.

Introduces nitrosylsulfuric acid, thereupon anhydrous. The reaction proceeds in this temperature range

Add hydrochloric acid while stirring constantly. 40 in front of you quickly enough and can be in 60 to 90 minutes

According to a special embodiment according to th are regarded as ended,
The end of the reaction can easily take place through the disappearance of nitrosylsulphuric acid also in portions by means of a spot reaction on the iodine metering device by means of a spot reaction on the iodine metering device by simultaneously determining the iodine potash starch paper,
The reaction can also be initiated under pressure in a substance. with anhydrous hydrogen chloride and olefin in the

The nitrosylsulfuric acid is generally loaded into the autoclave in prescribed proportions an equimolecular ratio to the olefinic in the presence or absence of a solution compound reacted, carried out in means, with persistent nitro-presence of at least 1 mole of anhydrous chlorine sulfate by means of a suitable metering device per mole of olefinic compound. One is joined.

However, the reaction can also take place in the presence of an excess of water

free hydrogen chloride or in excess of solvent, in which one or more reaction

olefinic compound or with an excess of partner are soluble, but in the above

the -chloroxime sulfate is insoluble only in hydrogen chloride or only in olefinic solvents,

Compound, based on the nitrosylsulfuric acid, the latter separates to form a white one

work. viscous oil from the liquid organic phase, and

The hydrogen chloride can also be formed »in situ«, the reaction product can therefore simply be through

be e.g. B. be separated by means of a reaction of an alkali chloride decantation. The reaction takes place

with sulfuric acid. 60 in a solvent in which the reaction product

In this case the nitrosylsulfuric acid is soluble in, the latter can be carried out at the end of the reaction

Dissolved sulfuric acid (molar ratio 1: 1) and the precipitation using a suitable diluent,

obtained solution to the suspended in the olefin such as benzene, carbon tetrachloride or petroleum ether,

Alkali chloride introduced. or by means of distillation of the used

The reaction between the olefin and the nitrosyl 65 solvent can be isolated under vacuum

Sulfuric acid is preferably used in the presence of The release of the α-chloroximes from the acidic

Solvents which are inert to nitrosyl sulphate - sulphates can also be used without the use of basic

led, wherein the reaction product, d. that reacting compounds take place, e.g. B. by

5 6

treated the acidic α-chloroxime sulfate with water. The connection obtained therefore corresponds to the

By filtration or extraction with a suitable formula:

Solvents such as methylene chloride, chloroform, NOH

Benzene, etc., one obtains the corresponding a-chlorine

oxime, which by means of crystallization or distillation ~ ^ - ^

■ can be cleaned further. 'r - Cl

Recommended according to a particular embodiment
to use a solvent that has both
α-chloroxime sulfate as well as the free α-chloroxime
able to dissolve and at the same time immiscible with water. 10 The refractive index is n ^s _D ° = 1.5057.
is cash. For this purpose, the IR spectrum of the

advantageous the use of methylene chloride made product has been found to be identical to the one made by proven. Mixing equimolar parts by weight 100%

The following examples are intended to provide a better explanation of sulfuric acid and pure α-chlorocyclohexanone oxime serve the invention. 15 obtained product proved.

To 113.5 g of the acidic «-chlorocyclohexanone oxime-

Example 1 sulfates are 200 cm ³ H ₂ O and 100 g crushed

Ice cream added. It separates as an upper layer

A glass flask of 500 cm ³ is charged with 50 g of cyclo-oily substance, which in a short time in solid crystal hexene (0.61 mol) and 150 g of cyclohexane. 20 linen state changes.
The glass flask is equipped with a reflux condenser, stirrer. It has also proven advantageous to extract the

factory, thermometer and two separate lines obtained white masses with methylene chloride er for hydrogen chloride and nitrosyl sulfate as well as with meadows. After the solvent has evaporated, an external cooling bath is provided. Once the cyclo-one as 64.3 g "-Chlorcyclohexanonoxim with a hexane-cyclohexene-mixture, the temperature of ⁰ ° C 25 melting point 73 to 75 ⁰ C, the following items has reached is having, stirring with the analysis:

Introduction of nitrosyl sulfate started and the same- Found .. C 49.1, H 6.5, Cl 23.7, N 9.65%;

early in the mixture of hydrogen chloride always in the low theoretical .. C 48.8, H 6.77, Cl 24.05, N 9.5%.

initiated in excess to nitrosyl sulfate.

In about 90 minutes, 60 g of nitrosylsulfur acid are acid (0.47MoI) and about 20 g of hydrogen chloride are calculated on nitrosylsulphuric acid or converted to (0.55 Mol) added. set cyclohexene, is 93.3 or 94.6% of the

In the course of the somewhat exothermic reaction, theory falls apart. The product recrystallized from petroleum ether turned into a whitish oil. After the end of the melts at 79 to 8O ⁰ C.
The reaction is stirred vigorously for about 30 minutes, 35 B '' 1 2

care must be taken that the temperature is constantly e 1 s ρ 1 e

remains at about 0 ^{° C.} Finally, the procedure as in Example 1 is removed by adding 50 g

Cyclohexane and the unreacted cyclohexene cyclohexene and 150 g CCl ₁ in a glass flask by simple decantation. 250 cm ^{3 are} thereby obtained. 60 g of nitro-complete, the cyclohexane and 12.1 g of cyclohexene-sylsulfuric acid are added in the course of 90 minutes, and at the same time it is recycled (determined by titration with bromine). the kept at a temperature of 0 ⁰ C react

The final mixture of 20 g of dry hydrogen chloride was sucked in under vacuum. Traces of cyclohexane and cyclohexene are removed and after the addition of nitrosyl sulfur is complete 113.5 g of product, the following elemental acid becomes the reaction mass for more analysis has stirred in comparison to the theoretical 45 30 minutes. During this period of time Analysis of an acidic α-chlorocyclohexanone oxime sulfate: the liquid phase turns blue. You get

110.1 g of oc-chlorocyclohexanone oxime sulfate and 11.2 g

Unreacted cyclohexene found. The «-Chlorcyclo-

C 29.3, H 5.1, N 5.4, S 12.5, Cl 14.0%; hexanone oxime sulfate has the described in Example 1

theoretically 50 benen chemical labels. The yield at

C 29.3, H 4.9, N 5.7, S 13.0, Cl 14.5%. acidic cyclohexanone oxime sulfate, calculated on the

converted cyclohexene is 95.2% of theory.

Due to its strong hygroscopicity, the sulfate is difficult to isolate in the solid state using the method described in Example 1, 60.7 g of oc-chlorocyclohexanone shimmering oil with a refractive index of 55 oxime with a melting point of 73 to 74 ^° C. appears The nf = 1.5070 and a density % - 1.504. Yield of pure «-chlorocyclohexanone oxime,

It is insoluble in aliphatic, cycloaliphatic traits on converted cyclohexene, is 87% and aromatic hydrocarbons such as petroleum- the theory,
ether, hexane, cyclohexane, cyclohexene, benzene, toluene Example 3

etc. Possible solvents are: methanol, 60

Ethanol, dioxane, acetone, acetic acid and methylene Proceed as in the previous example. In

chloride et al. The chemical composition of this case will be 60 g of nitrosyl sulfuric acid acidic a-Chlorcyclohexanonoximsulfates is also a solution of 50 g of cyclohexene in 150 g of acetic acid and by titrating the bound sulfuric acid thereupon a stream of dry hydrogen chloride has been confirmed. 65 passed through. The reaction temperature is initial

The yield of Chlorcyclohexanonoxim based +8 ⁰ C, towards the end of the reaction it is at +34 ⁰ C in nitrosylsulfuric acid is 98% and maintained at that. In this case, there is no separation of a converted cyclohexene, calculated: 99.5% of theory. oily product, but it creates a homogeneous one

clear blue colored solution. The above is diluted with cold water until no more precipitate occurs after further addition. The reaction mixture is extracted with methylene chloride. The solvent is removed by distillation under vacuum and the acetic acid and the unconverted cyclohexene are recovered in this way. There remains a solid residue of 58 g, which results by crystallization from petroleum ether, 52 g of pure a-Chlorcyclohexanonoxim melting at 79 to 8O ⁰ C.

Example 4

In a solution of 40 g of cyclohexene in 160 g of methylene chloride at 0 ° C in about 40 minutes * 5 while stirring 60 g of nitrosylsulfuric acid (molar ratio of nitrosylsulfuric acid to cyclohexene = 1: 1.03) was added and a stream of dry hydrogen chloride was passed in at the same time.

The result is a homogeneous liquid phase that has a slightly pale hue. The introduction of the hydrogen chloride is continued until the NO ⁺ ions disappear in the reaction mass. The reaction time is about 1 hour and 30 minutes. During this time a total of 19 g of hydrogen chloride are passed in. The reaction liquid can either be freed from methylene chloride, thereby obtaining the oc-chlorocyclohexanone oxime sulfate, or the procedure can be that 300 cm ^{3 of} ice-cold water are slowly poured into the above reaction liquid with constant stirring, the methylene chloride layer, which separates from the water freed and dried under vacuum without heating. The solid residue (64.2 g) consists of α-chlorocyclohexanone oxime with an oxime titer of 98% and a melting point of 77 to 78 ° C. The yield of α-chlorocyclohexanone oxime, calculated on nitrosyl sulfate, is 90.4% of theory.

Example 5

40

A solution of 30 g of 2-pentene in 90 g of cyclohexane is introduced into a glass flask measuring 250 cm ^3. The flask is equipped with a reflux condenser, stirrer, thermometer and two separate feed lines for hydrogen chloride and nitrosylsulfuric acid and also with an external cooling bath.

It is cooled to 0 ⁰ C and begins with the addition of nitrosyl sulfuric acid, comminuted and, by means of a metering device and simultaneously to a stream of gaseous hydrogen chloride passes, where it always works of the latter with a slight excess.

In about 120 minutes 44.2 g of nitrosylsulfuric acid and about 15 g of gaseous hydrogen chloride are produced introduced and reacted.

In the course of the reaction, which is a little exothermic, the initially brown-colored reaction mass becomes lighter and lighter with the formation of a whitish oil. The end of the reaction is determined by the disappearance of the reaction of the ion NO ⁺ through a spot reaction on iodine-iodine-potassium starch paper.

The cyclohexane is separated by decantation and the oil is extracted with fresh cyclohexane out, whereby the unreacted olefin can be recovered; by means of bromine titration 5.5 g of 2-pentene were determined in the cyclohexane extracts.

After removing the last traces of cyclohexane by applying a vacuum, 80.3 g are obtained of an oily product with the following elemental analysis:

C ₅ H ₁₀ ClNO · H ₂ SO,
Found .
calculated .

Cl 15.10, N 6.20, S 13.09%;
Cl 15.17, N 5.99, S 13.71%.

The product also has nl ° = 1.4815.

The reaction product, ie the acid sulphate of -chloro-n-pentanone oxime, is treated with water at 0 ° C. and then subjected to extraction with methylene chloride. After the extract has been dried using anhydrous magnesium sulfate, the solvent is removed by vacuum distillation, and the residue obtained is a liquid substance whose weight is 43.5 g, has a refractive index H ² S = 1.4720 and has the following elemental analysis: Cl = 26 , 50%; N = 10.90%.

Distillation under vacuum gives 42.9 g of a colorless tear-irritating liquid a boiling point of 75 ° C / 10mm Hg; raf? = 1.4723.

The elemental analysis shows for C ₅ H ₁₀ ClNO:

Found .... Cl 26.00, N 10.5%;
calculated .... Cl 26.14, N 10.33%.

The substance is identical to that through. Oximation of the 3-chloropentan-2-one obtained 3-chloropentan-2-one oxime.

The chromatographic analysis in the gaseous phase shows the presence of the pure 3-chloropentane-2-one oxime confirmed.

The absorption spectrum in the IR range has the following characteristic maxima (expressed in microns): 3.07, 6.05, 9.0, 9.25, 9.95, 10.35, 11.1, 12.1, 12.4, 12.8, 13.55, 14.85.

The yield of distilled S-chloropentane ^ -onoxime, calculated on converted 2-pentene, is 90.5% of theory.

Example 6

The procedure is as in Example 5, but 15 g of cyclopentene are dissolved in 50 g of cyclohexane.

24.5 g of nitrosylsulfuric acid and 8.5 g of gaseous hydrogen chloride are added in 1 hour.

After the reaction has ended, stirring is continued at 0 ^° C. for about 30 minutes. After this time interval has elapsed, the NO + ions have completely disappeared.

After separating off the cyclohexane and removing the last traces of the solvent in vacuo 43.70 g of an oily product of orange-yellow color are obtained, which the following elemental analysis having:

C ₅ H ₈ ClNO
Found
calculated

H ₂ SO ₄ :

.... Cl 15.20, N 5.79, S 13.50%;

.... Cl 15.30, N 6.04, S 13.83%.

40 g of this product, dissolved in methylene chloride, treated with water at ⁰ ° C. The methylene chloride layer is separated off, dried over anhydrous magnesium sulfate and the solvent is removed: a crystalline residue of 19.8 g of oc-chlorocyclopentanone oxime is obtained

having a melting point of 48 to 5O ⁰ C and the following elemental analysis:

C ₈ H ₈ ClNO:

Found .... Cl 25.90, N 10.40%; -

calculated .... Cl 26.54, N 10.48%.

Crystallization from petroleum ether increases the melting point to 52 to 53.5 ° C.

The analysis of the infrared absorption spectrum possesses the following characteristic maxima (expressed in microns): 3.05, 3.18, 8.25,10,33,10,58,11,15,11,55, 11.92, 12.2, 14.0.

The measurement was carried out with the KBr tablet.

The yield in α-chlorocyclopentanone oxime, calculated on the basis of nitrosylsulfuric acid, is 84% of ¹ S theory.

Example 7

A solution of 28 g of cyclooctene in 100 g of methylene chloride, which was kept at -10 ° C., was aa For 2 hours with stirring, 26 g of nitrosylsulfuric acid and about 9 g of gaseous hydrogen chloride fed.

Under these conditions, a homogeneous phase is obtained during the reaction which contains the reaction product in dissolved form; the solution takes on a pale yellow color during the reaction of the reactants, which remains until the end of the reaction. As soon as the disappearance of the ion NO ^{+ has been} determined by the spot reaction of iodine-KI starch papers, petroleum ether is added to the reaction mixture until the reaction product no longer precipitates.

The ether layer is separated and the amount of unreacted cyclooctene is determined by means of Titration. 0.5 g of cyclooctene were detected. The above separated product is in vacuo freed from the last traces of the solvent to constant weight: one receives 59.1 g oily product with the following elemental analysis:

C ₈ N ₁₄ ClNO · H ₂ SO ₄ :

Cl 13.00, N 3.90, S 11.60%;
Cl 12.95, N 5.11, S 11.71%.

Found
calculated

The product also has nf = 1.5100.

90.9 g of this substance, treated with water at 0 ° C, give after extraction with methylene chloride, Drying on anhydrous magnesium sulfate and evaporation of the solvent 30.1 g of oc-chlorocyclooctanone oxime with a melting point of 70 to 75 ° C.

The elemental analysis shows for C ₈ H ₁₄ ClNO:

Found .... Cl 19.95, N 8.02%;
calculated Cl 20.18, N 7.97%

After crystallization from petroleum ether, the melting point rises to 85 to 88 ⁰ C.

The analysis of the infrared absorption spectrum possesses the following characteristic maxima (expressed in microns): 3.13, 3.25, 6.06, 9.82, 10.12, 10.23, 10.72, 13.37, 13.88.

The measurement was carried out with a KBr tablet.

The yield of oc-chlorocyclooctanone oxime, on Calculated the converted cyclooctene is 80% of theory.

Example 8

The reaction is carried out in Example 7 with the only variant that a solution of cyclooctene in cyclohexane instead of methylene chloride. A-chlorocyclooctanone oxime is obtained with a Yield of 90.2% of theory based on the converted cyclooctene.

Example 9

The apparatus used in the previous examples is used.

A solution of 23.6 g of cyclododecene in 80 g of methylene chloride is added to the reaction glass vessel leads.

14.7 g of nitrosylsulfuric acid and 5 g of gaseous acid are added over 2 hours with stirring and at 0 ° C Add hydrogen chloride.

At the end of the addition of the reagents, the solution is orange-yellow in color. Stirring is continued until the NO ⁺ ion has completely disappeared (spot test with iodine-KI starch paper). The reaction product is precipitated with petroleum ether, and after the oily product has been separated off, the last traces of the solvent are removed under vacuum; 35 g of a dough-like red-brown product with the following elemental analysis are obtained:

C ₁₂ H ₂₂ ClNO
Found ,
calculated .

H ₂ OS.

Cl 10.09, N 4.50, S 10.35%;
Cl 10.74, N 4.24, S 9.71%.

After treatment with water at 0 ° C, the crystalline «-Chlorcyclododecanonoxim separated off, which comprises, after filtration, washing with cold water and drying under vacuum weighs 19.6 g and a melting point 131 to 132.5 ⁰ C.

The elemental analysis gives the following values:

C ₁₂ H ₂₂ ClNO:
Found .
calculated .

Cl 15.31, N 6.02%;
Cl 15.29, N 6.04%.

45 Analysis of the infrared absorption spectrum showed the following characteristic maxima (expressed in microns): 3.05, 3.18, 10.16, 10.5, 10.8, 11.95, 12.2, 12.7, 13, 16, 14.47.

The yield of α-chlorocyclododecanone oxime, calculated on the nitrosylsulfuric acid, is 74% of theory.

Example 10

55 The procedure is as in the previous examples.

A solution of

Introduced 20 g of 1-heptene in 60 g of cyclohexane. 22 g of nitrosylsulfuric acid and 7.5 g of gaseous hydrogen chloride are added over the course of 1 hour with stirring and at 0 ° C. Stirring is continued for 3 hours; After this time, the NO ⁺ ion has completely disappeared (spot reaction with iodine-KI starch paper).

The cyclohexane is separated by decantation and the oily layer is washed with fresh cyclohexane, to completely recover the unreacted olefin: from the cyclohexane extracts become

·. - ■ · 609727Z43 &

7.2 g of unreacted 1-heptene were determined by titration with bromine.

After removing the last traces of the solvent in vacuo, 40.5 g of an oily, slightly yellow colored substance, which is then treated with water at 0 ° C. It will now be a Extraction is carried out using methylene chloride and the combined extracts are rendered anhydrous Magnesium sulfate dried and then the solvent removed by vacuum distillation: 19.2 g of a yellow oil are obtained as residue.

By distilling this residue, 18.5 g of oc-chloronanthaldehyde oxime are obtained as a colorless liquid with a boiling point of 66 to 68 ° C./0.5 mm Hg and with n ^z i = 1.4658. The yield of distilled -chloronanthaldoxime, calculated on the converted olefin, is 86.7% of theory.

Claims (1)

Claim: 20th Process for the production of oc-chloroximes by converting a nitrosyl compound in Presence of anhydrous hydrogen chloride with an olefin of the general formula R ₂ wherein R ₁ , R ₂ and R _{3 are} hydrogen atoms, alkyls, cycloalkyls, aralkyls or aryls, or R ₁ and R ₂ or R ₁ and R _{3 are} a common cycloaliphatic closed _{by CH 2 groups.} Form ring with 4 to 12 carbon atoms, characterized in that the olefin is reacted ^{with nitrosylsulfuric acid at a temperature between about -30 and about + 3O 0} C, preferably at ^{0 0} C, and the a- Chloroxime is optionally released by adding water. Considered publications:
French Patent No. 1,220,685;
KA Hofmann, Textbook of Inorganic Chemistry, 1928, p. 169. 609 727/436 11.66 © Bundesdruckerei Berlin