DE1920499B2 - PROCESS FOR MANUFACTURING NITRILIUM CHLOROSULPHATES AND SOME NITRILIUM CHLOROSULPHATES - Google Patents

Description

pe «

OSO ₂ Cl)

R '[- C = NR "] [OSO ₂ Cl] _n

20 can be obtained in excellent yields. Acylation products of the type

RC = N-SO, OR ¹

where n is one of the numbers 1 or 2 and ßl in the case η = 1 is an alkyl radical with 1 to 8 carbon atoms, cyclohexyl, benzyl, phenyl or naphthyl radical and in the case w = 2 a C ₁ - to C _d - Alkylene, cyclohexylene, phenylene or naphthylene radical and R ¹ 'stands for a C ₁ - to Gr-alkyl radical.

30th

Aromatic and aliphatic nickel salts of the formula

[R- C = N- R'JX «

(R = alkyl, aryl; R ¹ = alkyl, aryl, acyl; Χ® = BF ₄ ©) are known. N-alkyl or N-aryl nitrilium salts were obtained for the first time by the action of triethyloxonium fluoroborate or aryldiazonium fluoroborate on aromatic and aliphatic nitriles [Ber. 89 (1956) 218].

The preparation of an N-ethylacetonitrilium salt has been described in a more recent work (Chem. Communications 1968, No. 23, p. 1533). Ethyl fluorosulfurate is used as the alkylating agent. The presence of a nitrilium salt (X® = OSO ₂ F, R = CH ₃ , R ¹ = C ₂ H ₅ ) could only be made probable by recording and interpreting the nuclear magnetic resonance spectrum.

The extraordinarily strong alkylating effect of the alkyl fluorosulfurate, as well as that of the Trifluormcthansulfonsäurealkylester recently produced (J. Qrg. Chem. 1965, 30 p. 4322) is on the the strong inductive effect of the fluorine atom. An acylating effect of the fluorosulfuric acid alkyl esters has not yet been observed, so that in the case of the alkyl fluorosulfate with a uniform course of the reaction (excluding alkylation) had to be expected.

In contrast, chlorosulfuric acid alkyl esters have an alkylating and acylating activity due to the lower binding energy of the SO ₂ —Cl group (Houben-Weyl, Methods of Org. Chemistry, Vol. VI / 2, Georg Thieme Verlag, Stuttgart, pages 466 C1

(R = alkyl, aryl, R ¹ = alkyl) could not be observed. As a result of the easy accessibility and simple handling of the lower chlorosulfuric acid alkyl esters, the discovery of this reaction ensures a broad range of preparative applications, especially since aliphatic and aromatic nitrilium salts are highly reactive intermediate compounds.

The invention therefore relates to a process for the production of nitrilium chlorosulfates, which is characterized in that one nitriles of the formula

R- [C ^ N] _n

where η denotes one of the numbers 1 or 2 and R in the case of η = 1 denotes an alkyl, aralkyl, aryl or cycloalkyl radical and in the case η - 2 denotes an alkylene, cycloalkylene or arylene radical, with an alkyl chlorosulfurate of the formula

Cl-SO ₂ OR ¹

wherein R ^{1 is} a lower alkyl radical, at about

0 to about 120 ° C.

The temperature range from about 20 to about 70 ^° C. is preferably used.

Another subject are nitrilium chlorosulfates of the formula

RT-C = NR ¹ I _n [OSO ₂ Cl] _n

where η is one of the numbers 1 or 2 and R 'in the case of n = 1 is an alkyl radical having 1 to 8 carbon atoms, cyclohexyl, benzyl, phenyl or naphlhyl radical and in the case η -2 a Ci-bisQ-alkylene, cyclohexylene -, phenylene or naphthylene radical

and R ¹ 'stands for a C ₁ - to C ₄ -alkyl radical.

The alkyl radicals R are both straight-chain and

also branched radicals with 1 to 20, preferably

1 to 8 carbon atoms are possible. Cycloaliphatic radicals are those with 5 to 12, preferably 5, 6 or 8 carbon atoms in the ring system. Aryl radicals are those with up to 20 carbon atoms in the Ring system, the phenyl or naphthyl radical being mentioned as preferred.

The ones used for the procedure Nitriles and dinitriles are known or can be obtained by known processes. Examples are:

Acetonitrile, Propionitrile, Butyronitrile, Capronitrile, Palmitic acid nitrile, Stearic acid nitrile, Malononitrile, Succinic acid dinitrile, Adipic acid dinitrile, Cyclohexyl cyanide, Benzyl cyanide, Benzonitrile,

p-tolunitrile,

a-naphthonitrile,

Tetraphthalic acid dinitrile.

The implementation of the method according to the invention is very simple. When using liquid aliphatic or aromatic nitriles, the reaction with chlorosulfuric acid alkyl ester can be carried out in excess of the former components.

Some of the nitriles mentioned are in particular at high temperature good solvents for the corresponding nitrilium salts. Partly crystallize the nitrilium salts in pure form after cooling and, if necessary, trituration of the reaction mixture the end. For the purpose of isolating the non-crystallizable aliphatic nitrilium salts, it is advisable to use them with a dry inert solvent, such as. B. ether, benzene or ligroin, from the reaction solution to fail. After washing several times with dry ether and then evaporating the still dissolved ether at room temperature in a vacuum, the highly reactive compounds are obtained in the form slightly yellowish oils. However, it is for the subsequent reaction of the nitrilium salts with nucleophilic agents more expedient to bring both reaction components in an equimolar ratio to the implementation. the solid or liquid nitrilium salts formed after the reaction has ended can then be used without further Cleaning operation suspended or emulsified in an inert solvent and then with the corresponding nucleophilic compound are reacted. Furthermore, the implementation both reactants in an equimolar ratio immediately with an inert dry solvent, such as B. ether, benzene, toluene, carbon tetrachloride, methylene chloride or chloroform, can be carried out. In the case of the use of dinitriles will be at least 2 moles of chlorosulfuric acid ester are used per mole of dinitrile.

The formation of two phases and the only faint odor of the chlorosulfuric acid alkyl ester then indicates the end of the reaction. Is carried out at an elevated temperature of 50 to 70 °, this is depending on the reactivity of the aliphatic or aromatic nitrile and the Chloroschwefelsäurealkylesters after ^l / ₂ to 2 hours the case.

The alkylation strength of the chlorosulfuric acid alkyl ester is known to decrease with the number of C atoms in the alkyl radical. The reaction can of course also be carried out at room temperature. The N-methyl-acetonitrilium salt of acetonitrile and Chlorosulfuric acid methyl ester is formed in good yield under these conditions after a few Hours, the N-methyl-benzonitrilium salt only after 2 to 3 days.

S The nitrilium chlorosulfates produced by the process according to the invention are highly reactive Intermediate products and can also be used directly as pesticides. The possibility of further implementations - they react in the

ίο meaning of the two boundary structures of the nitrilium ions

[RC = NR ¹ (a)

[RC = NR ¹ ] (b)

(R ~ alkyl, aryl; R ¹ = alkyl) - can be seen from the following statements:

Reactions of the boundary structure (a) predominate by far. This is for the numerous implementations of the Nitrilium salts with nucleophilic agents responsible. These include B. water, hydrogen sulfide, alcohols, mercaptans, primary or secondary aliphatic or aromatic amines, hydrazines and their derivatives, hydroxylamine. From the nitrilium

2s can be salted by reacting with appropriate nucleophilic reactants, for example, the following compounds are obtained: N-alkyl-acid amides, N-alkyl-thioamides, N-alkyl-imino ethers, N-alkyl-thioimnoethers, N-alkyl-amidines, N, N'-bis alkyl or N-alkyl-n'-aryl amidines. The mentioned Compounds form in good yield.

The reactions are exothermic, so that good cooling must be ensured. It is useful to combine the anion Cl — SO ₂ O ⁰ with the nucleophilic Partner primarily produced chlorosulfuric acid before processing the end products using dilute Neutralize alkalis. The general procedure is that after the nucleophilic partner has been added dropwise, the equimolar or Shot can be added, aqueous or alcoholic sodium or potassium hydroxide added and the reaction mixture is made weakly alkaline. The implementation options for the new connections are each following the execution examples of the method according to the invention explained.

example 1

A. Manufacturing of N-methyl-benzonitrilium chlorosulfate

103 g of benzonitrile (1.0 mole) and 40 g Chloroschwefelsäuremethylester (0.36 mol) are heated with stirring for ₂ to V% hour to 60 to 70 ⁰ C. After this time the odor of the chlorosulfuric acid is methyl esters only faintly perceptible. After this The N-methylbenzonitrilium chlorosulfate crystallizes out in the form of fine yellow needles when the reaction mixture is cooled and, if necessary, triturated. Due to the extremely high reactivity of the Salt must be suctioned off with the most careful exclusion of moisture. Obtains after 2 to 3 washes with dry ether about 55 g of the yellow stable compound with a melting point of 115 to 120 ° C.

If the above approach is carried out at room temperature, 3 to are obtained within 4 days after the described work-up, the N-methylbenzonitrilium chlorosulfate in the same yield.

B. Other implementations of N-methyl-benzonitrium chlorosulfate

χ. 27 g Chloroschwefelsäuremethylester (0.2 mol) and 20.6 g of benzonitrile (0.2 mol) are heated V ₂ hours at 7O ⁰ C s. On cooling, the N-methyl-benzonitrilium chlorosulfate crystallizes out as a solid yellow crystal cake. After suspension in 100 ml of dry ether, dilute sodium hydroxide solution is slowly added dropwise, while cooling with an ice bath and stirring, and the aqueous phase is made slightly alkaline. After the ether phase has been separated off and again etherified, the combined ether extracts are dried over Na ₂ SQ ₄ . The ether is evaporated in a vacuum. 22.5 g (ie 83% of theory) of a pale yellow oil are obtained, which immediately solidifies in a fully crystalline manner and can be recrystallized from benzene. Mp = 78 to 8O ⁰ C. (N-methyl-benzamide, m.p. lit. = 8O ⁰ C).

-NH-CH ₃

20th

β. If hydrogen sulfide is introduced into the above-mentioned N-methylbenzonitrilium salt-ether suspension and all acidic components are subsequently neutralized with dilute sodium hydroxide solution, about 15 g of a yellow-red oil with a boiling point of> ₀₅ = 135 are obtained after the described work-up and after distillation of the ether residue up to 150 ⁰ C, which soon solidifies in crystalline form. Recrystallization from dilute alcohol leads to slightly yellowish sulfur-containing needles, mp. = 76 ° to 78 ° C. (N-methyl-thiobenzamide, mp. = Lit. 79 ⁰ C).

35

CS-NH-CH ₂

y. 1, the Ba amount indicated in Example Chloroschwefelsäuremethylester with benzonitrile in the presence of 100 ml of dry benzene is heated ¹ J ₂ hour at 70 ° C, then immediately 2 phases form itself. The dropwise addition of methanol and subsequent neutralization with dilute sodium hydroxide solution gives, after conventional work-up, 29 g of an oily residue. 4s The distillation results in 18.5 g (62% ds d. Th.) Of a piercing-smelling liquid, bp. ₁₇ = 96 to 98 "C. (N-methyl-benziminomethyläther, bp. ₁₂ Lit. = 94-95 ⁰ C).

OCH ₃

ό. If the methanol used in Example IBy is replaced by 30 g of n-propylamine, about 30 g of an oily residue are obtained after work-up. The distillation results in an amine-like smelling liquid, bp. ₁₅ = 135 to 138 ° C, which soon solidifies and crystalline mp. 57 shows up to 6O ⁰ C. The titration with 1 η HCl and the analysis result clearly indicate the presence of an N-alkyl-N'-propyl-benzamidine.

NH-C ₃ H ₇

Example 2

20.6 g of benzonitrile (0.2 mol) and 29 g (0.2 mol) of ethyl chlorosulfuric acid are heated to 60 to 70 ° C. _{for 1 to IV for 2 hours.} After cooling, the N-ethylbenzonitrilium chlorosulfate crystallizes out in the form of yellow needles. (M.p. = 115 to 125 ° C). After suspension in 100 ml of dry ether, the mixture is made weakly alkaline with dilute sodium hydroxide solution while cooling in an ice bath. Customary work-up of the reaction mixture gives about 25 g of a yellow oil which solidifies in crystalline form and can be recrystallized from a little benzene. (M.p. = 65 to 67 ° C). Lit .: N-ethyl-benzamide, mp. = 68 ⁰ C.

Example 3

20.6 g of benzonitrile (0.2 mole) and 34.5 g chlorosulfonic acid n-butyl ester are held 2V ₂ hours at 70 ⁰ C. After cooling, the batch remains liquid and cannot be made to crystallize. When benzene is added, 2 phases form. The action of dilute sodium hydroxide solution results in a connection with a Κρ, _'Λ5 = 145 to 150 ⁰ C. According to analysis result and IR spectrum is Nn-butylbenzamide ago.

Example 4

50 g of dry acetonitrile (1.2 mol) and 30 g Chloroschwefelsäuremethylester (0.23 mol) '/ heated for 2 hour at 6O ⁰ C. After cooling, 100 ml of dry ether are added and the precipitated oily phase is washed again with ether. After evaporation of the residual ether in the oily phase in vacuo, the highly reactive N-methylacetonitrilium chlorosulfate is obtained in almost quantitative yield. This compound does not seem to be indefinitely stable at room temperature, so it is advisable to sell it with the desired partners as soon as possible. The action of equimolecular amount of water, subsequent neutralization with methanolic sodium hydroxide solution, suction of the precipitated Na ₂ SO ₄ and evaporation of the LösungsmittelsführtzuN-Methylacetamidvom Kp ^ ₂₀ = 105 ⁰ C. (Kp. = Lit. 206 ° C / 760 Torr)

Example 5

In an analogous manner, the conversion of 55 g of propionitrile (1.0 mol) and 29.0 g (0.2 mol) of chlorosulfuric acid thy lester results in the likewise oily still reactive N-ethyl propionitrilium chlorosulfate. The reaction with water as described in Example 4 leads to N-ethyl-propionamide, bp. ₁₃ = 104 to 106 ⁰ C (Kp. = Lit. 100 ° C / 10 Torr).

Example 6

After one hour of heating of 50 g dry acetonitrile (1.2 moles) and 20 g Chloroschwefelsäuren-butyl ester (0.12 mol) at 6O ⁰ C and Aurfällen with ether yields the Nn-Butylacetopitnliumchlorosulfat as an oily compound. The conversions with water, as described in Examples 4 and 5, lead to n-butylacetamide with a b.p. _w = 125 to 130 ° C. (b.p. lit. = 229 ° C. / 760 Torr).

Example 7

To 130.5 g of methyl chlorosulfurate (1.0 mol) 64 g of terephthalic acid dinitrile (0.5 mol, melting point = 224 to 226 ° Q in the) are added in portions at 70 to 80 ° C

7th

Measures added so that the reaction temperature of the stand (~ 133 g) is recrystallized from ethanol and the batch without external heat supply 80 ⁰ C does not rise above the N, N'-dimethyl-terephthalic acid formed. After the exothermic amide reaction has subsided, the mixture is rewained for a further 1 hour. After adding

dry ether gives the hygroscopic bis-5 _N

nitrilium chlorosulfate in the form of a viscous oil. To the ^H 3 ^< - ^HIN |

better identification is therefore under ice cooling I _

first with 100 ml of H ₂ O and then with con centered sodium hydroxide solution added, whereby a pH · value is set from 8 to 9. The now firm back ι ο isolated.

Claims (2)

Patent claims: 1. Process for the production of nitrilium chlorosulphates, characterized in that nitriles of the formula R- [C = N] _n where η denotes one of the numbers 1 or 2 and II in the case of n = 1 denotes an alkyl, aralkyl, aryl or cycloalkyl radical and in the case η = 2 denotes an alkylene, cycloalkylene or arylene radical, with an alkyl chlorosulfurate of the formula Cl-SO ₂ OR ^1, ₅ where R ^{1 is} a lower alkyl radical, at about 0 to about 120 ^° C. 2. Nitrilium chlorosulfate of the formula to 475, [1963]). In general, the properties of the organic fluorine compound due to the smaller atomic volume, the relatively high electron affinity and the low polarizability of the Fluorine atoms differ considerably from those of the other halogen compounds (Houben-W e y I, Vol. V / 3.1962, p. 398). As a result of the weaker Alkylation strength and the relatively high acylation effect must therefore be caused by the action of chlorosulfuric acid alkyl ester on aromatic and aliphatic nitriles at best too uninteresting in terms of preparation Lead reaction mixtures, surprisingly, however, it was found that even when using Chlorosulfuric acid alkyl esters nitrilium salts c