DE2401819C2 - Process for the preparation of sulfamic acid halides - Google Patents

Description

R ₁ -OH (M)

in which Ri has the aforementioned meaning with a halosulfonyl isocyanal of the formula O

Il

X-S-N = C = O (BT)

wherein X has the abovementioned meaning in an amount of 5 to 1000% by weight, based on the starting material HI, on aliphatic or cycloaliphatic hydrocarbons, aliphatic halogenated hydrocarbons, aliphatic or cycloaliphatic ethers and / or nitriles as solvents at -20 to + 140 "C unpressurized or implemented under pressure

It is known that N-Alkylamidosulfonylchloridc, by reaction of Monoalkylammoniumchloriden with sulfuryl chloride (Acta formerly Scand. 17 (1963). 2141). When performing the reaction in Presence of a strongly polar, organic solvent and addition of metal halide as catalyst could the reaction yields by the method described in German Patent 12 42 627 be improved. While the process gives good yields for lower, unconditional alkylamido sulfonyl chloride, the yields decrease with branching and with increasing chain length of the alkyl radical considerable. Haloalkylaminosulfonyl halides cannot be prepared in this way either. The long reaction time of the process, which is necessary for a satisfactory yield, is a disadvantage

Sulfuryl chloride must be used in considerable excess. Another disadvantage is the use of acetonitrile, which is not inert under the reaction conditions in the presence of hydrogen chloride occurs chlorination to trichloroacetonitrile, which trimerizes to trichloromethyltriazine (DE-PS 6 82391). That Some of the triazine distills off with the sulfamic acid halides, and some of it remains in the distillation residue. Especially in large-scale operations, these methods lead to processing difficulties, whereby

4S problems of environmental protection due to the high chlorine content of the by-products also play a role. In The German Offenlegungsschrift 19 43 233 discloses a process for the preparation of / i-chloroethylaminosulfonyl fluoride by halogen exchange of the corresponding aminosulfonyl chloride with hydrogen fluoride under pressure described. With regard to the reaction conditions and the two-stage reaction procedure via the first produced sulfonyl chloride is the process in terms of simple and economical operation, straight also on an industrial scale, unsatisfactory.

The German Offenlegungsschrift 21 64 176 describes a process for the preparation of sulfamic acid halides by reacting sulfamic acids with acid halides. Use is disadvantageous the comparatively expensive acid halides and the more difficult to access sulfamic acids. The procedure is with regard to environmental protection, avoidance of high amounts of salty or halogen-rich wastewater, simp rather and more reliable working method, although more suitable than the aforementioned processes, but on a large-scale scale not fully satisfactory.

All of these processes have in common that despite some good primary and secondary yields Alkylaminosulfonyl chlorides even more branched, z. B. tertiary compounds, so far on these routes were not accessible.

The invention now relates to the method shown in the preceding claim for the production of Sulfamic acid halides.

The reaction can be carried out if tert-butanol and chlorosulfonyl isocyanate are used reproduce the following formulas:

w (CHj) ₃ COH + O = C = N-SO ₂ Cl (CH ₃ ), C-NHSO ₂ Cl

Compared to the known methods, the method according to the invention was simpler and easier a large number of sulfamic acid analogues in better yield and purity

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In particular, tertiary alcohols, araliphatic secondary and tertiary alcohols and unsaturated primary, Secondary and tertiary alcohols are suitable as starting materials for this process and thus corresponding end products are available which are not produced by the previous processes or are produced only in poor yield could. The process is more environmentally friendly, more reliable and is based on easily accessible raw materials. All of these advantageous properties are surprising in view of the prior art.

Starting material II is mixed with starting material IH in a stoichiometric amount or with an excess of one or other starting material, preferably in a ratio of 1 to 1.05 mol of starting material II, based on Starting material IH, carried out The starting materials HI can by reacting with sulfur trioxide Cyanogen halide can be obtained. Fluorosulfonyl isocyanate and, in particular, chlorosulfonyl isocyanate are preferred

The starting materials II can be primary, secondary and preferably tertiary alcohols. Appropriate starting materials II and correspondingly appropriate end products I are those in whose formulas R _t denotes a straight-chain or branched alkyl radical having 3 to 20, in particular 3 to 8 carbon atoms, a cycloalkyl radical having 4 to 8 carbon atoms or an aralkyl radical having 7 to 12 carbon atoms, and X denotes a bromine or, preferably, chlorine atom. The radicals mentioned can also be replaced by groups and / or atoms which are inert under the reaction conditions, e.g. B. chloratonia, bromine atoms, alkyl groups with 1 to 4 carbon atoms, carbalkoxy groups with 2 to 4 carbon atoms, Cydoalkylgruppen with 4 to 5 carbon atoms, may be substituted. Appropriate end products I are in particular those in whose formula R a cydopentyl radical, cydoheptyl radical, cydobutyl radical, cyclooctyl radical, an alkyl radical with 2 to 5 substituted by chlorine atoms, bromine atoms, and cycloalkyl groups with 4 to 6 carbon atoms, a branched alkyl radical with 5 carbon atoms, the »1- MethyI-1-propyl radical, or an unsubstituted or substituted in the aforementioned manner Aikyiresi with 6 to 20, in particular δ to 9 carbon atoms and X denotes a bromine atom or chlorine atom

For example, the following alcohols II come into consideration: n-butyl alcohol, isobutyl alcohol, sea-butyl alcohol, Cyclobutyl alcohol, 1-ethyl-1-propyl alcohol, 1,2-dimethyl propyl alcohol, benzyl alcohol, n-pentyl alcohol, cyclopentyl alcohol, n-hexyl alcohol, phenyl ethyl alcohol, cyclohexyl alcohol, cycloheptyl alcohol, cyclooctyl alcohol hol, 2-methyl-1-ethyl-propyl alcohol, 1,2,2-trimethylpropyl alcohol, 13-dimethyl-n-butyl alcohol, 1,2-dimethyln-hexyl alcohol, 1-cyclohexylethyl alcohol.

However, starting materials II and, accordingly, end materials I, in the formulas of which X is a bromine atom, are preferred or in particular denotes a chlorine atom and Ri denotes the remainder

R ₄ -C-

R3

is, where R ₂ , R ₃ and R _{4 can be the} same or different and each represents an Aikyrest, in particular with 1 to 10 carbon atoms, a Cycioalkylrest, in particular with 3 to 8 carbon atoms, a Mono- or Polyhalogenalkyirest, in particular a Mono-, Di - or trichloroalkyl radical with 1 to 4 carbon atoms, an alkoxyalkyl radical, especially with 2 to 5 carbon atoms, an alkylthiolalkyl radical, especially with 2 to 5 carbon atoms, an aralkyl radical, especially with 7 to 12 carbon atoms, a phenyl radical, a naphthyl radical, an alkylphenyl radical, especially with 6 to 10 carbon atoms, an alkenyl radical or an alkynyl radical, in particular with 2 to 5 carbon atoms, or an alkylcarbonyl radical, in particular with 2 to 5 carbon atoms, an alkanonyl radical, in particular with 3 to 6 carbon atoms, R ₂ and R ₃ also together with the adjacent carbon atom members of a common, in particular 3- to 6-member or R ₄ and / or Rj can also each represent a hydrogen atom if R ₂ denotes an aryl radical or an aralkyl radical or an alkenyl radical or an alkynyl radical. The radicals and rings mentioned can also be inert groups and / or atoms, e.g. B. chlorine atoms, fluorine atoms, bromine atoms, nitro groups, alkyl groups with 1 to 4 carbon atoms, carbalkoxy groups with 2 to 4 carbon atoms, cycloalkyl groups with 4 to 6 carbon atoms.

The following alcohols are, for example, also suitable for the process according to the invention: tert-butanol, tert-amyl alcohol, 2-methyl-pentanol, 2,3-methyl-pentanol-3,2,3-dimethyl-2-butanol, 2-methylhexanol-2 , Triethylcarbinol, 3-methyl-hexaπol-3,2 _r 3-dimethylpentanoI-3,

2,4-dimethylpentanol-2,2,2,3-trimethyl-butanol-3,2-methyl-heptanol-2,4-methyl-heptanol-4,

Z ^ -Dimethyl-hexanol ^^ - Dimethyl-hexanol ^ W-Dimethyl-hexanol - ^ - Methyl-S-ethylpentanol- ^ 2-methyl-3-ethyl-pentanoi-3,2-methyl-octanol-2,2, 5-dimethyl-heptanol-5 ₁ 2-methyl-4-ethyl-hexanol-4, 2,4,4-trimethyl-hexanol-2,2-methyl-nonanol-2, tripropyl-carbinol, 3-ethyl-octanol- 3, 2-methyl-5-ethyl-heptanol-5,2,4,6-trimethylheptanol-4,1-methyl-cyclopentanol-1,

1 -Methyl-cyclohexanol-1, dimethyl-cyclopropylcarbinol, methyl-ethyl-cyclopropyl-carbinol,

1 -Methyl-cycloheptanol-1,1-ethyl-cyclohexanol-1,1-ethyl-cycloheptanol-1,1 ^ -dimethyl-cyclohexanol-1, l ^ -Dimethyl-cyclohexanol-M-Isopropyl-l-methyl-cyclohexanol-i ^ -Methyl-decanol ^, 2-methyl-undecanol-2, chloro-tert.butanol, U-dichloro ^ -methylpropanol ^, 13-Dicπlor-2-methyl-propanol-2,1,1,1 -Trichlor ^ -methyi-propanol ^, bromo-tert-butanol, iChl ^ thlbl ^ SChl ^ hlbl

yyo,
Bisehlormethyl-ethyl-carbinol, 1-chloro-2-methyl-pintanol-2,2-chloro-3-methyl-pintanol-3,
S-chlorine - ^ - dimethyl-buianol - ^ - chlorine-S-ethyl-penlanol-J, l, 1, U ^ 3-Hxafluoro-2-methylpropanol-2.
2-Mclhyl-3,3,4,4-tetrafluorobuianol-2, Mcth () xy-lcil.-buianol, 4-methyloxy-2-methylbutanol-2,

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Phenyloxy-terL-butanol, methyllhio-terL-butanoI, Phcnykhio-terL-bulanoKit / t-dimethylbenzyl alcohol.
, «-Methyl-benzyl alcohol, 2-methyl-4-phenyl-butanol-2,2-methyl-S-phenyl-propanoW,

Ethyl-phenylcarbinoUMethyl-benzyl-carbinoLp-chlorobenzyl-dimethylcarbinoI, benzhydrol,
2-naphthyl-propanol-2,2-p-toluyl-propanoI-2,2-methylbuten-3-ol-2, 3-MeUIyIbUtIn-S-Ol ^ crotyl alcohol,

. 5 Methallyl alcohol, butene-1-ol-3, dimethyl-acetylcarbinol or diacetone alcohol.

The reaction is carried out at a temperature of -20 to +140 ⁰ C, in particular from 10 to 80 ⁰ C ₁ under atmospheric or superatmospheric pressure, continuously or discontinuously. Aliphatic halogenated hydrocarbons, especially chlorinated hydrocarbons, are used in the reaction. B. tetrachlorethylene, 1,2-dichloropropane, tetrachloroethane, carbon tetrachloride, chloroform, trichloroethane, trichlorethylene, pentachloroethane, cis-Di _r 'io chloroethylene, 1,2-dichloroethane, methylene chloride, 1,1-dichloroethane,! ^ - cis-dichloroethylene , n-butyl chloride, 2-, 3- and iso-butyl chloride, 1,10-dibromodecane, 1,4-dibromobutane; aliphatic or cycloaliphatic ethers, e.g. B. n-butyl ethyl ether, di-n-butyl ether, di-iso-amyl ether, diisopropyl ether, cyclohexyl methyl ether, diethyl ether, tetrahydrofuran, dioxane, #i? '- dichlorodiethyl ether; Nitriles such as acetonitrile, aliphatic or cycloaliphatic hydrocarbons, ζ. B. pentane, hexane, heptane, nonane, «-pinene, pinane, ο-, m-, p-cymene, gasoline fractions, in particular with a boiling point of 70 to 190 ⁰ C, cyclohexane, methylcyclohexane, petroleum ether, decalin, ligroin, 2A4 -Trimethylpentane _r 223-trimethylpentane, 233-trimethylpentane, octane; and corresponding mixtures. The solvent is used in an amount of from 5 to 1000% by weight, preferably from 200 to 500% by weight, based on the starting substance III.

The reaction can be carried out in the following manner: A mixture of the starting materials and the solvent is kept at the reaction temperature for 0.5 to 2 hours. Dar? is from the - mixture of the end product in the usual way, z. B. by removal of the solvent or fractionated destination, isolated. In a preferred form, chlorosulfonyl isocyanate is allowed to run in, starting at room temperature, to a solution of the aforementioned alcohols II in the solvent according to the invention and the temperature of the mostly exothermic reaction is allowed to rise ^{to 30 to 50 ° C.} As soon as half of the isocyanate has been added, the elimination of carbon dioxide is generally increased, so that, depending on the evolution of gas, the second feed is carried out at a temperature of 10 to 40 ^° C. The reaction temperature depends on the ease of decarboxylation; in most cases, e.g. B. In the case of saturated, tertiary aliphatic alcohols, it is sufficient to heat to 45 to 55 ° C for 10 to 30 minutes after combining the components. A pH indicator, for example, is used to convince oneself that the split-off gas consists predominantly of carbon dioxide; As soon as larger amounts of hydrogen chloride are split off, the heating is stopped. If the decarboxylation is too slow, e.g. B. in unsaturated alcohols, may optionally be heated above 80 ⁰ C addition.

The known and new compounds which can be prepared by the process of the invention are valuable Starting materials for the manufacture of pesticides, dyes and pharmaceuticals. So you can

z. B. from them by reaction with anthranilic acid or its salts in the German Offenlegungsschrift 21 04 682 produce described o-sulfamidobenzoic acids. By cyclizing these substances, e.g. B. after the in the German Offenlegungsschrift 21 05 687, one arrives at the 2,1,3-benzothiadiazin-4-one-2,2-dioxides, their use for pesticides and pharmaceuticals in the same patent application, in DE-AS 15 42 836 and in the German Offenlegungsschrift 23 49 114 is further described Use is shown in Belgian patents 7 57 886 and 7 02 887 and DE-PS 11 20 456. The end products I can also be used as starting materials for fungicides (DE-OS 19 53 356). Also from the End products 1 according to the invention by reaction with glycolic anilides in the German Offenlegungsschrift 22 01 432 described herbicides available. From the end products I can dip by hydrolysis. corresponding Halogenamines are manufactured, the starting materials of chemotherapeutic remedies on the Area of combating cancer and tumors are (Ullmanns Encyklopädie der technischen Chemie, Volume 10, pages 773 ff). From the substances I one obtains according to the in Arzneimittelforschung 12 (1962), pages 1119 ff. described method N-halogen and N.N-bis-d ^ -halogenalkylJ-sulfamidhydrazones, which against sarcomas and carcinomas are effective.

The end products I already have a herbicidal effect themselves and are particularly suitable for killing barnyard millet are effective:

2-Csilor-2-methyl-propyl- (3) -aminosulfonyl chloride,
l-chloro-butyl- (2) -aminosulfonyl chloride,
2-chloro-butyI- (3) -aminosulfonyl chloride,
2-chloro-cyclohexyl-aminosulfonyl chloride.

The parts listed in the following examples are parts by weight.

example 1

At 20 ° C., half of 283 parts of chlorosulfonyl isocyanate are dissolved in a solution of 176.3 parts of tert-amy.'alko-

hol run in 1200 parts of petroleum ether (boiling point 70 to 80 ⁰ C) so that a temperature of "0 adjusts itself to 56 ° C. The rest of chlorosulfonyl isocyanate was added under cooling at 15 to 2O ⁰ C; the total addition time is 40 minutes. Now the mixture is 10 minutes at room temperature and 10 minutes at

M 60 "C. The reaction mixture is then stirred in vacuo. During the distillation

(120 'CVO, 1 Torrjerhii ¹ ! Man 2b2 parts (70.7% of theory) lori.Ai.iykiniiiiosiilfoiiyk-nloricl with /? "- 1.4MiI.

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Example 2

If the reaction is carried out as in Example 1 in η-hexane, the same end product is obtained in the same yield and Preserve purity.

Example 3

If, as in Example I, 283 parts of chlorosulfonyl isocyanate are added to a solution of 148.2 parts of tert-butanol ■ in 1000 parts of η-hexane, 317 parts (92.4% of theory) of tert-butylaminosulfonyl chloride are obtained Kp 85 "00.05 Torr; n ² ₀ ⁵ - 1.4579.

Example 4

170 parts Chlorsulfonylisocanat is allowed with stirring over 35 minutes first at 40 "C and then with vigorous elimination of carbon dioxide at 20 ⁰ C a solution of 130.3 parts of chlorine-tert-butanol in 550 parts of petroleum ether overflow. Subsequently the mixture is heated 45 minutes 75 ° C until the gas has been split off. When the reaction mixture is concentrated, 247 parts (practically quantitative) of chloro-tert.-butylami-

nosulfonyl chloride with a boiling point of 75 to 85 ° C / 0.05 torr with η £ = 1.4819.

Example 5

128.5 parts of chlorosulfonyl isocyanate are allowed to one-third at 35 ° C. and stirring within 30 minutes two thirds at 20 to 25 ° C with cooling a solution of 127.7 parts of a / t-dimethylbenzyl alcohol in 350 parts of η-hexane run in. To complete the decarboxylation, the mixture is stirred for 20 minutes at 45 ° C. Concentration in vacuo leaves 200 parts (95% of theory) Λ, Λ-dimethylbenzylamino-

sulfonyl chloride with n "= 1.5628.

Examples

170 parts of chlorosulfonyl isocyanate is allowed over 25 minutes to a stirred solution of 146.6 parts of λ · Methyl-benzyl alcohol in 500 parts run η-hexane with slight cooling so that the internal temperature of 20 ⁰ C at the end of the reaction down to 50 ⁰ C increases. The mixture is stirred for 15 minutes at 65 ° C. and then concentrated in vacuo, 258 parts (98% of Thcroic) <x-methylbenzyiaminosulfonyl chloride being added

n ' _o ^s = 13398 can be obtained. 1R spectrum: characteristic wave numbers: NH 3300cm- ', SO ₂ 1185, 1390cm-', G ₁ H ₅ -700.760cm- ·, CHi-2970cm-ι.

40

Example 7

To a solution of 86.6 parts of methyl alcohol in 490 parts of η-hexane, the mixture is left with stirring at 40 bis 45 ° C run in half of 170 parts of chlorosulfonyl isocyanate. The remainder is then fed in at 20 to 30 ° C; the total addition time is 25 minutes. The reaction mixture is then stirred at 70 ° C. for 50 minutes.

After concentration in vacuo, 196 parts (= 96% of theory) of methallylaminosulfonyl chloride are obtained as a viscous oil. Its IR spectrum shows the following characteristic wave numbers: NH 3220 cm- ', SO ₂ 1370, 1150 cm-', C = C 940 cm- '.

Examples

As in Example 7, 170 parts of chlorosulfonyl isocyanate are added to a solution of 86.6 parts of crotyl alcohol in 490 parts of η-hexane, 155.5 parts (76% of theory) of crotylaminosulfonyl chloride are obtained. In the IR spectrum, the SOr bands appear at 1370.1170 cm- 'and the C = C band at 965 cm-'.

55

Example 9

148.2 parts of lerL-Buianol are left within 45 minutes, first half at 25 to 30 ° C., then at 45 to 55 ° C to a solution of 283 parts of chlorosulfonyl isocyanal in 2250 parts of 1,2-dichloroethane run. That The reaction mixture is stirred for 20 minutes at 60 ° C., a little solid is filtered off with suction and concentrated in vacuo 298 parts (87% of theory) of lerL-butylaminosulfonyl chloride with a boiling point of 83 ° to 87 ° C./0.02 torr are obtained.

Example 10

If, analogously to Example 1, 170 parts of chlorosulfonyl isocyanate were converted with a solution of 139 parts of diacetone alcohol in 500 parts of η-hexane, 249 parts (97% of theory) of 4-methylpentan (2) -one-4-yl-aininosulfonyl chloride were obtained as viscous OIL Its IR spectrum shows the following characteristic wave numbers: NH 3150 cm - '. C = 01710 cm -', SO ₂ 1350.1150 cm- '. §J

5 p

Claims (1)

Claim: Process for the preparation of sulfamic acid halides of the formula R ₁ -NSX CO I I! HO in which Rt is an aliphatic, cycloaliphatic or araliphatic radical and X is a haloalom denotes characterized in that one uses an alcohol of the formula