DE2008116A1 - Per substd allophanic acid halide prepn - Google Patents

Abstract

Persubstd. allophanic acid halides R1R2N-CO-NR3-CO-X (I) (where R1 and R2 are aliphatic or opt. nuclear-substd. araliphatic or aryl groups; and R1 and R2 together with N can form a 5-, 6- or 7-membered heterocyclic ring where a 6-membered ring can contain also an O atom as heteroatom; and R1 and R2 together can also denote =C(Cl)Y (where Y is H, Cl, methyl, CH2Cl-, CHCl2- or CCl3-, opt. halogen- or CF3-substd. phenyl or unsubstd. naphthyl); R3 is an aliphatic or opt. substd. araliphatic group and X is halogen), are useful as intermediates for plastic additives and plant protective agents. They are prepd. by reacting carbamoyl halides R1R2NCOX with isocyanates R3NCO in presence of catalysts, pref. halides of first four Sub-group elements and of Main group IV or V, or tertiary amines, at -50 to +200 degrees C (pref. 0-120 degrees C, partic. 20-90 degrees C), pref. in presence of a solvent.

Description

Persubstituted allophanoic acid halides are the subject of the invention are new allophanoic acid halides and a process for their production.

Persubstituted allophanoic acid halides include such derivatives of allophanic acid to understand that there are no free hydrogen atoms on the nitrogen atom own.

A generally applicable process for making persubstituted Allophanoic acid halides are not yet known. So far it is not special succeeded in adding carbamic acid chlorides to isocyanates.

The invention relates to a process for the preparation of persubstituted Allopbanic acid halides, which is characterized in that one carbamic acid halides and isocyanates in the presence of halides of the elements of the first four subgroups or the fourth and fifth main group of the periodic table or of substances, which are at least partially converted into such halides in the reaction mixture or in the presence of tertiary amines, optionally in the presence of a solvent, at temperatures from -50 ° to + 2O00C.

The procedure can be explained as follows: The majority of the carbamic acid halides that can be used for the process correspond to the general formula wherein the radicals R1 and R2 can be the same or different and represent aliphatic and optionally substituted araliphatic and aryl radicals, furthermore R¹ and R² in the case of alkyl radicals can be part of a 5-, 6- or 7-membered heterocyclic together with the nitrogen atom Be ring system, which in the case of the 6-ring can also contain an oxygen atom as a further heteroatom, furthermore R1 and R2 can be used together for the remainder where Y is hydrogen, chlorine, methyl, a mono-, di- or trichloromethyl group, a phenyl group optionally substituted by halogen (preferably chlorine or bromine) or a trifluoromethyl group and an unsubstituted naphthyl group and X is halogen.

As aliphatic radicals (R1 and R2) are except straight-chain or optionally branched-chain alkyl radicals with 1 to 6, preferably 1 or 2 carbon atoms, To understand alkenyl radicals with 3 to 6 carbon atoms and cyclohexyl radicals. Possibly substituted araliphatic radicals and aryl radicals are preferably benzyl and Phenyl radical.

Halogens (preferably fr'luor, Chlorine, bromine), lower alkyl radicals (preferably 1 to 3 carbon atoms), lower Alkoxy groups (preferably 1 to 3 carbon atoms) and optionally together with one or more of the abovementioned radicals, a nitro group in consideration.

Most of the isocyanates used in the process corresponds to the general formula - - N = CO II where R3 is an aliphatic as well one if necessary.

substituted araliphatic radical means.

The aliphatic radicals (R3) are straight-chain or optionally branched-chain alkyl radicals with preferably 1 to 18, in particular 1 to 6 carbon atoms, Alkenyl radicals with in particular 3 to 6 carbon atoms (preferably 3 carbon atoms), Cycloalkyl radicals with 5, 6, 8 or 12, preferably 5 or 6 carbon atoms in Understanding the ring system.

The araliphatic radicals (R3) contain 1 to in the aliphatic part 4, preferably 1 or 2 carbon atoms and as an aromatic radical in addition to the naphthyl preferably the phenyl radical. As a substituent in the core of the araliphatic The rest In addition to halogens (preferably fluorine, bromine, chlorine), there are also lower alkoxy groups (preferably 1 to 4 carbon atoms) and alkoxycarbonyl groups with up to 4 (preferably 1 or 2) carbon atoms in the alcohol component.

The new compounds obtainable by the process correspond to the general formula in which the radicals R1, R2, R3 and X have the meaning given above.

Preferred new compounds (III) are those in which a) the radicals R1, R2 are alkyl radicals having 1 to 6 carbon atoms and R3 is alkyl having 1 to 18 carbon atoms and X is chlorine, b) the radicals R1 and R2 together - = CC12 and R3 is an alkyl radical having 1 to 6 hydrocarbon atoms and X is chlorine, c) the radicals R1 and R2 together represent the group Y stands for hydrogen, chlorine, methyl, a mono-, di- or trichloromethyl group, a phenyl group optionally substituted by halogen (preferably chlorine or bromine) or a trifluoromethyl group and an unsubstituted naphthyl group and R3 stands for alkyl with 1 to 6 carbon atoms as well as the allyl radical and X is chlorine, d) the radicals R¹ and R2 together C1 = 14 3 6.Koh- mean and where R3 stands for alkyl having 1 to lenstoffatomen and for the allyl radical and X stands for chlorine.

Catalysts for the purposes of the invention are halides of the elements of the first four subgroups of the periodic system (Mendelejef) and the fourth and fifth main group and tertiary amines such as trimethylamine, triethylamine, benzyldimethylamine, tributylamine, N-methylpyrrolidine, N-methylpiperidine. The following substances may be mentioned as examples of catalytically active halides: CuCl, HgCl2, SnCl2, SnCl4, SbCl5, TiCl4, ZeCl2, CuBr, ZnBr2, but other inorganic compounds of the same elements or organic salts such as

or metal powder, t.B. Zinc powder, which is in the reaction mixture at least partially converted into halides, serve as catalysts. The ones to be used Catalyst quantities are between about 0.01 and 10 percent by weight of the reaction mixture, preferably 0.5 to 3%.

The carbamic acid halides for the reaction are the N-halocarbonyl compounds, in particular the N-chlorocarbonyl compounds of amines, of the general formula suitable, in which R¹ and R2 have the meaning given above. Examples of such carbamic acid halides are: dimethyl, methylethyl, diethyl, methylhexyl, diallyl, cyclohexylmethyl, methyl-4-chlorobenzyl, methyl-2- methoxyphenyl, ethyl-3-tolyl, tetramethylene, pentamethylene, 3-oxapentamethylene or diphenylcarbamic acid chloride.

In addition, the following carbamic acid chlorides, for example, are also suitable for the reaction: CHCl = N-COCl CCl2 = N-COCl CH3-CCl = N-COCl CHCl2-CCl = N-COCl CCl3-CCl = N-COCl Carbamic acid chlorides, including the last-mentioned types, are known, for example from "Angewandte Chemie International Edition, Vol. 1, 1962, No. 12, p. 633".

Isocyanates which can be used for the reaction according to the invention aliphatic and optionally substituted araliphatic isocyanates such as e.g. Nethyl, ethyl, propyl, allyl, 2-chloroethyl, methoxymethyl, hexadecyl and Octadecyl isocyanate and araliphatic isocyanates such as benzyl or 2-phenylethyl isocyanate as well as 4-methyl-benzyl isocyanate, 2-chloro-benzyl isocyanate, 3-nitro-benzyl isocyanate, 2-phenyl ethyl isocyanate and α- naphthyl methyl isocyanate.

Isocyanates suitable for the process are e.g. in Annalen 562, p. 75-136, (1949).

Solvents that can be used are those that do not react with the used Carbamidsaurechlol; id still react with the isocyanate, e.g. if necessary Hydrocarbons substituted by halogen or nitro groups, ethers, esters, Nitriles, sulfones or sulfonic acid esters.

In the simplest case, the process can be pressureless and with or little above room temperature by mixing the reactants and the catalyst be carried out without solvent with dissipation of the heat of reaction.

In general, a temperature range of about -50 ° to + 203 ° C. is preferred a temperature from 0 ° to t-120 ° C., in particular 200 to 90 ° C., is possible.

The carbamic acid chlorides and isocyanates are preferred in approximately equimolar amounts are used, but it is also possible to use an excess of one Component to use. The order in which the two components are added is on not critical. But it can if a slightly trimerizing isocyanate is used be expedient, the latter in a solution or suspension of the catalyst instilled in the carbamic acid chloride, the chloride used in excess can be.

Occasionally it is also useful to use a catalyst solution - if necessary at the same time as the isocyanate to drop the carbamic acid chloride into it.

Before working up, it can be useful to change the catalyst used to remove or inactivate.

This can be done, for example, by adding anhydrous sodium carbonate or sodium acetate and, if necessary, suction or by pouring into ether or petroleum ether and filtering off happen. The isolation or purification of the reaction products he follows in the usual way, e.g. by distillation or crystallization and suction.

Of course, the process can also be carried out continuously will.

The persubstituted allophanoic acid halides obtained are new Substances that are used as intermediates for numerous syntheses, e.g. for the production of plastic auxiliaries and pesticides can be used.

In the following examples, the temperature data relate to to ° C.

Example 1: 5 ml of SnCl4 are added dropwise to a mixture of 107.5 g (1 mol) of dimethylcarbamic acid chloride and 70 g of methyl isocyanate at 30.degree.-35.degree. After standing overnight at 20-250, it is poured into 0.8 liters of ether, filtered and the solvent is distilled off in the vacuum. The liquid residue is then distilled on a thin-film evaporator at 800 jacket temperature and 0.08 to 0.1 Torr, after which it is pure enough to give 76 g (46, c ') trimethylallophanoic acid chloride when fractionated on a still with a boiling point of 700 / 0.08 Torr and a refractive index nD20: 1.4810.

Example 2: Analogously to Example 1, tetramethylene or. Pentamethylene carbamic acid chloride and methyl isocyanate, the following allophanic acid chlorides Kp: 100 ° / 0.08 Torr nD20: 1.5045 Kp: 100 ° / 0.08 Torr nD20: 1.5058 Example 3: In a mixture of 321 g (2 mol) of N-dichloromethylene carbamic acid chloride and 115 g of methyl isocyanate 20 ml of triethylamine were quickly added dropwise. The mixture is refluxed for 12 hours, the temperature rising from 55 ° to 79 °. After cooling, it is poured into 1 liter of petroleum ether, filtered and fractionally distilled. 187 g (43%) of the compound are obtained OH C12C = N-CO-t-CO-Cl index and: 1.5140.

with a boiling point of 62 ° / 0.2 Torr and refraction from the same carbamic acid chloride, the following compounds are obtained with n-propyl or allyl isocyanate using an analogous procedure Bp. 650 / 0.08 Torr nD20: 1.5000 and Bp. 60 ° / 0.04 Torr nD20: 1.5115 Example 4: A mixture of 80 g of N-dichloromethylene carbamic acid chloride, 28.5 g of methyl isocyanate and 3 g of SnCl2 (dried) is refluxed until a temperature of 900 is reached is, after adding 5 g of methyl isocyanate again up to 900 and after adding a further 5 g of methyl isocyanate until a reflux temperature of 1200 is reached. After pouring into ether and filtration, it is distilled. 26 g (24%) of the are obtained link CC12 = N-004C0-C1 boiling point 54 ° / 0.1 Torr; nD20: 1.5142 Example 5: A solution of 2 ml of SnCl4 in 10 g of N-dichloromethylene carbamic acid chloride is added dropwise to a boiling mixture of 150.4 g of N-dichloromethylene carbamic acid chloride and 130 g of ethyl isocyanate, whereupon the reflux is maintained for a further 5 hours will. After pouring into 400 ml of ether and filtering, 114 g (49.5%) of the compound are obtained by distillation with a boiling point of 66 ° / 0.08 Torr and refractive index nD20: 1.5020.

Example 6: In a mixture of 40.4 g (Q, 2 mol) of phenylchloromethylene carbamic acid chloride and 19 g of methyl isocyanate are added dropwise 1 ml of SnCl4 at 20 to 400 within 2 hours. After four hours of stirring, pouring into 200 ml of ether and filtering, 37 g of the compound are obtained by distillation on a thin-film evaporator at 11150 jacket temperature and a pressure of 0.1 Torr of boiling point, 95 ° / 0.07 Torr and refractive index 20: 1.5845.

The yield is 71.5% of theory. Theory.

Claims (11)

Patent claims: 1. Persubstituted allophanoic acid halides of the formula wherein the radicals R¹ and R² can be the same or different and represent aliphatic and optionally substituted araliphatic and aryl radicals, furthermore, in the case of alkyl radicals, R1 and R2 can be part of a 5-, 6- or 7-membered heterocyclic ring system together with the nitrogen atom be, which in the case of the 6-ring can also contain a hydrogen atom as a further hetero atom, furthermore R1 and R2 can together for the remainder where Y is hydrogen, chlorine, methyl, a mono-, di- or trichloromethyl group, a phenyl group optionally substituted by halogen or a trifluoromethyl group and an unsubstituted naphthyl group, R³ is an aliphatic and an optionally substituted araliphatic radical and X is halogen. 2. Compounds according to claim 1, wherein the radicals R1 and R represent alkyl radicals with 1 to 6 carbon atoms and R3 for alkyl with 1 to 18 carbon atoms and X means chlorine. 3. Compounds according to claim 1, wherein the radicals R¹ and R² together = CCl2 and R3 is an alkyl radical having 1 to 6 carbon atoms and X means chlorine. 4. Compounds according to claim 1, wherein. the radicals R1 and R2 together for the grouping Y stands for hydrogen, chlorine, methyl, a mono-, di- or trichloromethyl group, a phenyl group optionally substituted by halogen or a trifluoromethyl group and an unsubstituted naphthyl group and R³ stands for alkyl 1 with 6 carbon atoms and the allyl radical and X is chlorine . 5. Compounds according to claim 1, wherein the radicals R1 and R2 together and where R3 is alkyl having 1 to 6 carbon atoms and the allyl radical and X is chlorine. 6. Compounds according to claim 1 j. Process for the preparation of persubstituted allophanoic acid halides, thereby ; e denotes that carbamic acid halides and isocyanates are used in the presence of Converts catalysts at -50 to + 200 ° C. 8. The method according to claim 7, characterized in that one carbamic acid halides of the formula wherein the radicals R¹ and R² can be the same or different and represent aliphatic and optionally substituted araliphatic and aryl radicals, furthermore, in the case of alkyl radicals, R1 and R2, together with the nitrogen atom, can form part of a 5-, 6- or 7-membered heterocyclic ring system be, which in the case of the 6-ring can also contain an oxygen atom as a further heteroatom; furthermore, R1 and R2 can be used together for the remainder stand, where Y is hydrogen, chlorine, methyl, a mono-, di- or trichloromethyl group, a phenyl group optionally substituted by halogen or a trifluoromethyl group and an unsubstituted naphthyl group and X is halogen and isocyanates of the formula R³-N - N = CO wherein R³ denotes an aliphatic and an optionally substituted araliphatic nest; used. 9. The method according to claim 7 and 8, characterized in that one as catalysts halides of the elements of the first four subgroups as well as the fourth and fifth main group of the periodic table or tertiary amines are used. 10. The method according to claims 7, 8 and 9, characterized in that that the reaction is carried out in the presence of a solvent. 11. The method according to claims 7, 8, 9 and 10, characterized gekennzeivhnet, that one is working in the temperature range from 0 to 120 ° C.