DE1206901B - Process for the preparation of alkyl tin isocyanates and isothiocyanates - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

GERMAN

PATENT OFFICE

EDITORIAL

Int. CL:

C07f

German class: 12 ο - 26/03

Number:
File number:
Registration date:
Display day:

St21914IVb / 12o
April 1, 1964
December 16, 1965

The invention relates to a process for the preparation of Alkylzinnisocyanaten isocyanates and isothiocyanates, which is characterized by heating a Alkylzinnoxyd or hydroxide having 1 to 18 carbon atoms per alkyl radical with urea or thiourea at temperatures above 130 ^0C.

In organotin chemistry it is known that bis-trialkyltin oxides cleave when they with various substances with active hydrogen atoms, e.g. B. acids, phenols, enols, imides or Amides. In these reactions, the reactants usually get together heated, and an alkyl tin component replaces an acidic hydrogen atom and thus becomes part of the acidic Component bound, with water escaping as a by-product.

Attempts have now been made to produce further organotin derivatives by the process described. Included a mixture of bis-tributyltin oxide and urea was heated to form a tributyltinurea in which one of the hydrogen atoms of the urea molecule is replaced by a tributyltin residue would be replaced. However, the reaction did not produce the expected N-tributyltin urea. Instead it was obtained a colorless liquid with a boiling point of 110 ° C / 0.4 Torr. A chemical and infrared analysis this material was found to be tributyl tin isocyanate. Though the reaction several times using various organotin oxides including the trialkyltin oxides and -hydroxyde was carried out, one obtained in each case in place of the expected organotin urea the trialkyl tin isocyanate. It has also been found that urea is differentiated by its sulfur analog, i.e. H. Thiourea, can be replaced, whereby a trialkyl tin isothiocyanate is obtained. The course of the new Discovered reactions can be represented schematically by the following chemical equations, in which X stands for O or S:

Process for the production of
Alkyl tin isocyanates and isothiocyanates

Applicant:

Stauffer Chemical Company, New York, N.Y.

(V. St. A.)

Representative:

Dr. W. Beil, A. Hoeppener and Dr. H. J. Wolff,

Lawyers,

Frankfurt / M.-Höchst, Adelonstr. 58

Named as inventor:

Walter Stamm, Tarrytown, N. Y. (V. St. A.)

Claimed priority:

V. St. v. America April 2, 1963 (269 888)

(C ₄ Hg) ₃ SnOSn (C ₄ H ₉ ) S + 2 (H ₂ N) ₂ CX

> 2 (C ₄ Hg) ₃ SnNCX + H ₂ O + 2NH ₃

(C ₂ H ₅ ) ₃ SnOH + (H ₂ N) ₂ CX

> (C ₂ H ₅ ) ₃ SnNCX + H ₂ O + NH ₃

From the equations it can be seen that in the formation of the trialkyl tin isocyanate ammonia and Water.

The reaction can also be effected by means of a dialkyltin oxide and a urea component.

In the latter case, a substance is obtained which consists of a polymeric complex of a dialkyltin oxide with a dialkyltin diisocyanate. While the trialkyl tin isocyanates and isothiocyanates in the Can be vacuum distilled are the complexes derived from urea and dialkyltin oxides Organotin isocyanates waxy solids with a relatively high melting range. According to the chemical analysis and the infrared spectrum, it is believed that the chemical Structure of the dialkyltin oxide-dialkyltin diisocyanate complexes described can be represented by the following formula:

[(R) ₂ SnO • (R) ₂ Sn (NCO) ₂ J _n

where R is an alkyl radical having 1 to 18 carbon atoms and η is an integer greater than 2. In the preparation of the alkyl tin isocyanates and isothiocyanates, excellent results can be achieved if the starting compounds are in an inert atmosphere, e.g. B. nitrogen, heated. One convenient method is to melt about 1 mole of trialkyltin oxide and about 2 moles of urea together. When using a dialkyltin oxide, the molar ratio is

509 758/466

3 4

Organotin to urea 1: 1. Preferably, the reaction product should have been at reduced

the temperature only slightly above the temperature distilled off pressure from the reaction vessel, and one which to melt the reactants a colorless liquid received by Kp _{0 (3} = 102 ⁰ C; is required, so is the production of trialkyl n "-.. 1.488 The yield was 52 g (78%)

performed in the range of 170 to 180 ⁰ C. Normal-. .

wisely, the reaction is carried out until the Ji e ι s ρ ι e 1 3

molten urea phase has disappeared and triethyl tin isocyanate

the evolution of ammonia gas has ceased. In io (C ₂ H ₅ ) SnNCO

In some cases it may be desirable to keep the reactants in the molten state after the evolution of ammonia.
ensure the completeness of the reaction. Colorless distilled Triäthylzinnisocyanat The ver-Trialkylzinnisocyanat at or isothiocyanate 15 reduced pressure (bp. _{0> 4} = 7O ⁰ C) in 91 ° / _o sodium Ausdann will yield by vacuum distillation or by extraction. The product crystallized in the container (melting ion with organic solvents from the reaction point 34 ⁰ C). The infrared spectrum showed a very isolated ion mixture, strong band at 2190 cm- ¹ , also the elementary

In the preparation of the dialkyltin oxide dialkyl analysis, the proposed structure was confirmed.
tin diisocyanate complexes will react on 20

carried out in a similar manner, but one uses an.

Instead of trialkyltin oxide, a dialkyltin oxide. Im B e 1 s ρ 1 e 1 4

In general, excellent results can be achieved [(C ₄ Hg) ₂ SnO · (C ₄ H ₉ ) ₂ Sn (NCO) ₂ ] "

achieve when you use the dialkyltin oxide and the

Urea in approximately equal molecular amounts 25 25 g (0.1 mol) of insoluble, powdered dibutyl melt. To produce the dialkyltin oxide-dialkyltin oxide, temperatures in the pulverized urea were mixed with 6.1 g (0.1 mol) of dry tin diisocyanate complexes. The mixture range from 170 to 190 ⁰ C is recommended. was slowly heated up to 175 ° C. At this

Temperature melted the mixture to a clear,

. 30 viscous oil (dibutyltin oxide does not melt under

Example 1 320 ⁰ C). It was kept for 1 hour at 18O ⁰ C.

Tri- (n-butyl) tin isocyanate ammonia and ammonium carbonate were combined in one

(nC ₄ H ₉ ) ₃ SnNCO cold trap collected.

The reaction product was a waxy solid

A reaction vessel equipped with stirrer, thermometer 35 having a melting range 190-210 ⁰ C and meter, nitrogen inlet tube, vent tube and soluble in alcohols. The infrared spectrum showed an oil heating system was fitted with 600 g (1 mole) of very strong bands at 2180 cm- ¹ . Tin and nitrogen tributyltin oxide and 125 g (2.05 mol) fine powder analyzes confirmed the composition of the above-mentioned dry urea charged. The formulated dibutyltin oxide isocyanate.
slurry was slowly heated to 125 ° C 40 with stirring

heated, and at that point development continued. .

of ammonia. The reaction mixture became example

Maintained at 140 ^° C. for 1 hour, and a moderate tri-n-butyltin isothiocyanate

A stream of N _{2 was} bubbled through the reaction mixture, (nC ₄ H ₉ ) ₃ SnNCS

to remove all H ₂ O and NH ₃ . After a 45
The gas evolution ceased for an hour. 7.65 g (0.1 mol) of anhydrous, finely powdered thio

The crude reaction product, a colorless liquid urea containing 30 g (0.1 mol) of bis (tributyltin) property, was purified by vacuum distillation. mixed oxide. The mixture was heated with pure tri- (n-butyl) tin isocyanate distilled at 110 °. It melted at 170 ⁰ C and was 1 hour at up to 115 ° C / 0.4 to 0.5 Torr. It was kept in the form of a 50 at this temperature. While the bath is colorless liquid in 82% i§ ^ei "yield (540 g) kept at 175 to 185 ° C, vacuum was applied condition; nf = 1.490 and the reaction product through a 50 cm high.

Column at 120 to 130 ° C / 0.15 Torr in about 50%

. -ίο Yield (17 g) distilled overhead. About 12 g

Example _{2 g5 n} j cnt converted bis (tributyltin) oxide were used as

Tri- (isobutyl) tin isocyanate higher-boiling fraction at 140 to 150 ° C / 0.15 Torr

(iC ₄ H ₈ ) ₃ SnNCO recovered.

Tri- (n-butyl) tin isothiocyanate is a clear, colored

12.2 grams of dried, powdered urea (0.2 moles) loose liquid; nff = 1.519. Its structure was mixed with 60 g (0.1 mol) of bis (triisobutyltin) oxide 60 by elemental analysis and by a very strong one. The mixture was confirmed to have an absorption band of 2020 cm- ^{1 with stirring.}
140 ⁰ C heated. Within about an hour the tributyltin isocyanates are excellent catalysts

all urea dissolved, and the gas evolution generators for the production of polyurethane foams stopped. The mixture was held an additional hour at from diisocyanates, glycols or glycol ethers and 140 ⁰ C. 6 g (NH ₄ ) SCO ₃ (which was formed from 2NH ₃ 65 water. Trialkyl tin isocyanates are also active + H ₂ O + CO ₂ ) were collected in the same pesticide and in this separator, which is in direct connection with their usability as a leaf and connection with the reaction vessel. Fungicides as well as weed and indoor

Claims (3)

5 6 sect repellants for pre- and post-treatment with urea or thiourea on temperatures mentioned. heated above 1300C. Claims: 2 Process according to Claim 1, characterized in that one organotin oxides or -hy- 1. Process for the production of Alkylzinniso- 5 droxyde used. cyanates and isothiocyanates, thereby 3. The method according to claim 1, characterized indicates that one draws an alkyltin oxide that one mole of a dialkyltin oxide or hydroxide with 1 to 18 carbon atoms per alkyl radical is reacted with 1 to 2 mol of urea. 509 758/466 12.65 © Bundesdruckerei Berlin