DE1204225B - Process for the preparation of N, N ', N "-triorganoborazoles which are halogen-substituted on boron - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

GERMAN

PATENT OFFICE

EDITORIAL

Int. α .:

C07d

German class: 12 ο -26/01

Number: 1204 225

File number: F 44085IV b / 12 ο

Filing date: September 29, 1964

Opening day: November 4, 1965

The invention relates to a method of manufacture of N, N ', N "-triorganoborazoles which are halogen-substituted on boron.

Halogenated «B-Hydrogen-N-triorganoborazoles are valuable intermediate products for the production of highly stable polymers and additives for fuels based on hydrocarbons, plasticizers and flame retardants.

A number of processes have become known which allow the production of partially or perhalogenated Describe borazoles. However, these processes either only achieve low yields or work under relatively unfavorable conditions. In some cases, only those that are perhalogenated on boron can be used Obtain borazole. .

The German Auslegeschrift 1091549 or 1118174 describes the production of N, N ', N "-trihydrogen-B, B', B" -trichloroborazole from boron trichloride and ammonium chloride at 150 to 170 ° C. in a fluidized bed. According to Journ. Chem. Soc, 1960, p. 4028, N, N ', N "-triphenyl-B, B', B" -trichloroborazole can be obtained in 70% yield by heating N-phenyl-B-trichloroborazane in benzene. The same process can also be used for the preparation of the lower alkyl compounds according to Journ. At the. Chem. Soc, 82, 89 (1960), e.g. B. N, N ', N "-triethyl-B, B' ₃ B" -trichloroborazole is available in 52% yield. N, N ', N "-Trihydrogen ~ Β, Β', Β" - trihydrogenborazole reacts according to Ber., 73, p. 209 (1940), with chlorine at high temperatures to a white sublimable product of unknown composition during the reaction with bromine to Ν, Ν ^ Ν "- Trmydrogen-B-hydrogen-B ^ B" - dibromoborazole. The reaction of the above compound with boron trichloride or boron tribromide led to Journ. Am. Chem. Soc, 73, 1612 (1951 ), r to mixtures of mono- and di-halosubstituted Borazolen in 35% yield ^e.

According to J. inorg. Chem., 1.1962, pp. 93 to 98, it is not possible to combine B, N, N ', N "-tetramethylborazole and Β, Β', Ν, N ', N" -pentamethylborazole with CCl ₄ , N-chloro -succinimide or CuCl ₃ to chlorinate. Only the reaction with HCl leads in a reaction analogous to the reaction with borazole (cf. Chem. Ber., 73, 1940, p. 221), but only when high pressures are used to give the corresponding boron halogen derivatives.

Another reaction is also known (Chem. Ber., 94, 1961, pp. 671 to 676) in which aminoborazoles are converted into trichloroborazole and the corresponding amides in a smooth reaction with boron trichloride or phosphorus oxychloride.
Furthermore, in the German interpretation process for the production of boron
halogen-substituted
N, N ', N "-triorganoborazoles'

Applicant:

Paint factories Bayer Aktiengesellschaft,

Leverkusen

Named as inventor:
Dr. Karl John, Leichlingen

1162 363 proposed a method in which N, N ', N "-triorgano-B, B', B" -trihydrogenborazole are reacted with phosphorus pentahalides. at However, only the corresponding Β, Β ', Β' '- trihalogenborazoie are obtained with this process.

The invention now relates to a method of manufacture 'of N, N', N "-triorganoborazoles which are halogen-substituted on boron, characterized in that is that one NjN '^ - Triorgano-B ^ B ^ trihydrogenborazoles the general formula:

(HB-NR) ₃ ,

in which R denotes alkyl, alkenyl, halogen-substituted alkyl, halogen-substituted alkenyl, cycloalkyl, halogen-substituted cycloalkyl, alkyl-substituted cycloalkyl, aryl, halogen-substituted aryl and / or alkyl-substituted aryl radicals, with 'acid halides, sulfur or three carbon mono-halides Phosphorus at temperatures above 0 ⁰ C, preferably at 60 to 150 ⁰ C converts.

Depending on the ratio in which the reactants with the above halogenating agents are brought to reaction, the corresponding tri-, di- or monohaloborazoles are formed in good yields that can be separated by fractional distillation or crystallization.

The halogenating agents used in the new process are preferably:

COCl ₂ , SO ₂ Cl ₂ , SOCl ₂ , S ₂ Cl ₂ , SCl ₂ , PCl ₃ .

With SO ₂ Cl ₂ and S ₂ Cl ₂ , the derivatives of borazoles perchlorinated on boron are obtained in a smooth reaction, while the other halogenating agents can preferably be used to prepare the derivatives partially chlorinated on boron. In addition to the chlorine-containing halogenating agents mentioned above, leave

509 720/43 *

I 204 225

3 4

other halogen derivatives, such as PBr ₃ , example 2

Use S ₂ Br _2. In a three-necked flask with a stirrer, immersing

The nitrogen atoms of the boron thermometers, drip tray and reflux condenser to be halogenated are

azoles can e.g. B. carry the following residues: the 824 g (6MoI) phosphorus trichloride heated to 75 ° C

5 and at this temperature with constant stirring 82.4 g

As alkyl groups e.g. B. (0.5 mol) N, N ^ N '' - triethyl-B, B \ B '^ trihydrogenbör-

Methyl, ethyl, n-propyl, isopropyl, dodecyl, azole were added dropwise _{in IV 8 hours.} The mixture will

Stearyl residues; 5 hours to complete the HCl elimination

as alkenyl groups ζ ^refluxed B. After cooling and filtering

τ. ι αii ι A Li j. ίο will take the excess phosphorus trichloride

Propenyl, allyl, crotyl radicals; Normal pressure distilled off and the residue about

as halogen-substituted alkyl groups e.g. B. _eme column fractionally distilled. Be there

2-chloroethyl, 2-bromoethyl radicals; 88 g N.N '^ - triethyl-B.B'-dicHor-B ^ monohydro-

as cycloalkyl groups e.g. B. genborazol, b.p. _{0> 1} 40 ° C obtained, corresponding to a

Cyclohexyl- or alkyl- or halogen-substituted ¹ S yield of 76% of theory.

Cyclohexyl radicals; and B ₃ N ₃ C ₆ H ₁₆ Cl ₂

as aryl groups z. B. Calculated ... 30.36% Cl, 13.89% B;

Phenyl or. Naphthyl residues or their alkyl or found ... 30.1% Cl, 13.9% B.

halogen-substituted derivatives. _20th

The implementation can be carried out in an inert example 3

Solvent or suspending agent as well as by

direct ^{bringing together of the reactants through ϊη a} three-necked flask with stirrer, immersing

be guided. Chlorinated aliphatic or aro- ² S a solution of 82.4 g (0.5 mol) of Ν, Ν ', Ν''- triethyimatic hydrocarbons, such as. B. symmetrical B, B ', B "-trihydrogenborazole in symmetrical tetra-tetrachloroethane, tetrabromoethane, chlorobenzene or chloroethane heated to 70 ° C and at this temperature m-dichlorobenzene etc. are used. ²⁰³ S (1.5 mol) sulfuryl chloride within 1 hour

To carry out the procedure can, for. B. the solution is added dropwise. The mixture is to complete a Β, Β ', Β''- heated Trihydrogenborazols in tetrachloro- ³ ° HCl and SOG development 3 hours under ethane while introducing phosgene and Alloca- vigorous stirring at 80 ⁰ C. After filtration of heat and reacted with vigorous stirring ^and removal of the solvent, the residue will be. In general, fractional distillation ^{takes place over a} column in the temperature range. In this case, of 60 to 18O ⁰ C, a sufficiently rapid halo 104 g of N, N ', N "-Triäthyl-B, B', B" -trichlorborwasserstoffentwicklung instead. Azole to complete 35 Kp. _{O> is} 76 ⁰ C, corresponding to a From "the elimination of the hydrogen halide, the yield of 78% of theory.
Reaction mixture after addition of the halogenation B ₃ N ₃ C ₆ H ₁₆ Cl ₃

by means of about 3 to 4 hours with stirring and calculated ... 39.68% Cl, 12.11% B;

Passing an inert gas through to the reaction temperature. , _ίή . '". .._' V ₃

held. After the reaction mixture has cooled down * ° «emuden ... jy, 4S /„ u, i2, z / ₀ ts.
the solvent is stripped off in vacuo and

the residue is fractionally distilled through a column - Example 4

lates.

In another embodiment of the process Iu a double-necked flask with stirrer, immersing

but may also rank the halogenating agent presented advertising 45 thermometer, and Tropftriehter Rückfiußkühler and borazole with good stirring was added dropwise to 714 g (3MoI) of thionyl chloride at 75 ⁰ C heated. Z.3 is here. when using phosphorus and at this temperature a solution of 134 g of phosphorus trichloride the use of a solution or. Sus- (0.5 mol) N, N ', N "-Tri- _i S'clilöräthyM, B', B" -trihydro pension agent not necessary. genborazole in symmetrical tetrachlorethylene inside

The following examples explain the invention as half an hour added dropwise. The mixture becomes the

Proper procedures: HCl elimination for about 6 "hours at reflux et *

. -I ₁ heats Then the excess TMonyl-

Example 1 removed chloride and solvent and the return

In a three-necked flask with stirrer, eintauchen- ^st and fractionated over a column. The thermometer and reflux condenser are in a 55 117 g Ν, Ν ', Ν "- tri - β - chloroethyl - B« monochlor solution of 82.4 g (0.5MoI) Ν, Ν', Ν '' - Triethyl B, 'B "-dihydrogenborazole bp. _{0 (2} 112 to 114 ⁹ C, er-Β, Β', Β" - trihydrogenborazole in symmetrical tetra- hold, corresponding to a yield of 77.9% of the chloroethane at 7O ^{Phosgene introduced at 0} C. The mixture theory,
_{B 3} N ₃ C ₆ Hx ₄ Cl ₄ is added with constant introduction of phosgene and stirring

heated to 135 to 145 ⁰ C in 4 hours. After ^cooling off 6o τ ^, λ, ", * Λ (\ τ \ αι ώ aarqoi ptcooling, the solvent is drawn off in vacuo"'. _{Λ n} , _ _Ae . .- ",% ,,

and found the residue fractionated over a column ". 11.1% B _s 46.45 / ₀ CL
distilled. 25 g of N, N ', N "-Triäthyl-

B-monochior-B ', B "-dihydrogenboerazole, b.p. ₃ 65 ° C and example 5

76 g ^^^ "- triethyl-BB ^ dichloro-B ^ -monohydro- 6 ₅

Genborazol, bp ₃ 82 ⁰ C obtained, corresponding to a In a three-necked flask with stirrer, immersed yield of 90% of theory of halogenated thermometer, dropper ^ and reflux condenser wer-borazoles. the 202.5 g (1.5MoI) disulfur dichloride to 8O ⁰ C

10

heated and at this temperature 82.5 g (0.5 mol) of N, N ', N "-triethyl-B, B', B" -trihydrogenborazole were added dropwise within 2 hours. After 3 hours heating at 80 to 9O ⁰ C. The cooled solution is filtered and the residue after removal of the excess Dischwefeldichlorids fractionated over a column. This gives 95.5 g of N, N ', N "-triethyl-Β, Β', Β" - trichloroborazole, b.p. _{0> 15} 76 ⁰ C, "corresponding to a yield of 71.3%

Example 6

In a three-necked flask equipped with a stirrer, immersed thermometer, dropping funnel and reflux condenser, to 82.5 g (0.5 mol) of N, N ', N "-triethyl-B, B', B" -trihydrogenborazole at 6O ⁰ C 170 g ( 1.65 mol) of sulfur dichloride was slowly added dropwise. The mixture is then ^{heated to 100 to 105 °} C. for 3 hours. After cooling and filtering, the excess sulfur dichloride is drawn off and the residue is fractionated on a column. 43.2% Ν, Ν ', Ν "- ao triethyl-BjB'-dicHor-B ^ monohydrogenborazole, boiling point ₃ 48 to 50 ° C, and 39.2% N, N', N" -triethyl -B, B ', B "-trichloroborazole, b.p. _0> i ₅ 76 ° C.

30.36% Cl, 13.89% B;
31.1% Cl, 14.0% B.

Calculated
found

39.69% Cl, 12.11% B;
39.3% Cl, 12.3% B.

Claims (2)

Patent claims: 1. Process for the preparation of N, N ', N "-triorganoborazoles which are halogen-substituted on boron, characterized in that N, N ', N "-triorgano-B, B', B" -trihydrogenborazoles of the general formula (HB-NR) ₃ , in which R denotes alkyl, alkenyl, halogen-substituted alkyl, halogen-substituted alkenyl, cycloalkyl, halogen-substituted cycloalkyl, alkyl-substituted cycloalkyl, aryl, halogen-substituted aryl and / or alkyl-substituted aryl radicals, in the case of sulfur or acid halides, or tri-carbon, phosphorus halides Temperatures above O ⁰ C, preferably at 60 to 150 ⁰ C converts. 2. The method according to claim 1, characterized in that the reaction with COCl ₂ , SO ₂ Cl ₂ , SOCl ₂ , S ₂ Cl ₂ , SCl ₂ or PCl _{3 is} carried out. Calculated
found Considered publications:
German interpretative document No. 1162 363.