DE1077227B - Process for the preparation of spirophosphoric acid ester halides and spirothiophosphoric acid ester halides - Google Patents

Description

The invention relates to a process for the preparation of spirophosphoric acid ester halides and Spirothiophosphoric acid ester halides of the general formula

P - shark

c ' XH 2-0, Z ' ^v - ^X CH - 0 Z

in Z a tetrahydropyranyl- (2) -, 3,4-dialkyl- or 3,3,4,4 - tetraalkyltetrahydropyranyl - (2) -, tetrahydropyranyl - ^) -, 2,4-dialkyl or 2,2,4,4-tetraalkyltetrahydropyranyl (3) radical 'Z' means one

- CRR '- CRR' - CH ₉ - CH, - O -

there-

or - CRR'-0 -CH ₂ -CH ₂ -CRR 'radical
represents, in which R and R 'are hydrogen atoms or alkyl groups, X is an oxygen or sulfur atom and Hal is a chlorine or bromine atom. The individual alkyl groups preferably contain 1 to 8 carbon atoms.

A compound produced according to the invention is, for. B. the spiro - {[2-chloro-2-oxo-4- (3 ", 4" -dimethyltetrahydropyranyl-2 ") - 1,3,2-dioxaphosphorinane] -5,2 '- (3', 4 ' -dimethyltetrahydropyran)} of the following formula:

Method of manufacture
of spirophosphoric acid ester halides

and
Spirothiophosphoric acid ester halides

Applicant:

Union Carbide Corporation,
New York, NY (V. St. A.)

Representative: Dr. W. Schalk, Dipl.-Ing. P. Wirth,

Dipl.-Ing. G. E. M. Dannenberg

and Dr. V. Schmied-Kowarzik, patent attorneys,

Frankfurt / M., Große Eschenheimer Str. 39

Claimed priority:
V. St. ν. America January 3, 1956

William Morton Lanham, Charleston, W. Va.

(V. St. A.),
has been named as the inventor

CH ₂ -O

/ (6Ί (10

CH ₂ '5')

\ W) (3Ί

^ CH-CH

C Hq CHq

^υ \ it

(1) \ H

- Cl

H) 3ι

XH - O

a temperature between 25 and 60 ° C with diols is now characterized in that the phosphorus oxychloride or bromide or phosphorothiochloride or bromide with diols of the general formula

CH-CHCH,

i Z 'C

Od "

n ».CHCH,

CH ₉ OH

XHOH

CH ₂ -XH ₂

Patent 1,051,279 already relates to a process for the preparation of spirophosphoric acid ester halides and spirothiophosphoric acid ester halides using phosphorus oxyhalides and phosphorothiohalides, respectively with 1,3-diols.

The process according to the invention for the preparation of the above-mentioned spirophosphoric acid ester halides and spirothiophosphoric acid ester halides by reacting phosphorus oxychloride or bromide in the presence of a inert organic solvent at a temperature between 10 and 40 ° C or phosphorothiochloride or bromide in the presence of an inert organic solvent and a hydrogen halide binder in Z a tetrahydropyranyl- (2) -, 3,4-dialkyl- or 3,3,4,4-tetraalkyltetrahydropyranyl- (2) -, tetrahydropyranyl- (3) -, 2,4-dialkyl or 2,2,4,4-tetraalkyltetrahydropyranyl (3) radical and Z 'denotes a

CRR '- CRR'

CH ₂ - CH ₂ - O-

or CRR '- O - CH ₂ - CH ₂ - CRR' radical in which R and R 'are hydrogen atoms or alkyl groups.

The diols used as starting material are in an known way by dimerization of acrolein or an /? ~ alkyl- or -dialkyl-substituted acrolein, subsequent aldol condensation of the aldehyde obtained and hydrogenation of the unsaturated condensate obtained

909 759/423

sation product. These methods are described in U.S. Patents 2,479,284, 2,481,377 and U.K. Patent specification 667 131 described, or they form the subject of German patent 953 525.

In the inventive reaction of the diols with a phosphorus oxyhalide, equimolar amounts are preferably used Amounts are used, although any of the reactants can also be present in excess. The phosphorus oxyhalide is preferably a solution of the diol in an inert solvent such as Benzene added; the addition can, however, also be carried out in reverse without any adverse effect will. The addition is usually carried out by bringing the reaction mixture to 25 ° C. at a pressure of 500 mm is held. Atmospheric pressure can also be used and this is then used to remove the by-product the resulting hydrogen halide can be reduced. The obtained spirophosphoric acid ester halide can be easily purified by crystallization from ethyl ether or another inert solvent; however, this is not necessary unless an excess of diol is used. The reaction product is obtained as a residue in practically quantitative yields and high purity.

The inventive reaction of the diols with a phosphorothiohalide is preferably carried out at 40.degree carried out, the exothermic reaction being easy and rapid. The reaction is in the presence of a inert diluent, preferably a hydrocarbon of the benzene series, carried out. Preferably the phosphorothiohalide is added dropwise with stirring to a solution of an equimolar amount of the Diol and the theoretical amount of the tertiary amine added in benzene solution. If necessary, a benzene solution of the diol of the solution of the phosphorothiohalide in pyridine and benzene are added. Any of the reactants can be used in excess. The reaction mixture is made with water washed to remove the last remnants of the amine hydrohalide. It becomes a practically pure spirothiophosphoric acid ester halide obtained as a residue. If necessary, this is further purified by recrystallization from a solvent such as diethyl ether.

The following examples illustrate the invention.

example 1

To a solution of 461 g (2 mol) of 2-Methyloltetrahydropyranyl - (2) - tetrahydropyranyl - (2 ') - carbinol is held in 400 cc of benzene, the mm at a pressure of 500 to 25 ⁰ C, with stirring for 37 307 g (2 mol) of phosphorus oxychloride were added dropwise in minutes. After the reaction mixture has been kept at this temperature and pressure for a further hour, the pressure is reduced to 350 mm for 1 hour and finally to less than 2 mm at 25 ° C. for 44 hours. The pressure is then less than 2 mm at 45 ° C. for 1 hour, the spiro - {[2-chloro-2-oxo-4-tetrahydropyranyl- (2 ") - 1,3,2-dioxaphosphorinane] -5,2'-tetrahydropyran}

, CH,

-O

CH ₂

P-Cl

C Hn O Hq

XH-CH ₉

CH ₉

is obtained as a solid residue in a yield of 618 g (theoretically 621 g). The characteristics are as follows: F. 145 to 15O ⁰ C, purity (by esterification) = 98.7%.

Found
calculated

9.70,
9.97,

Cl

11.04,
11.42,

46.70,
46.39,

6.74;
6.49.

Example 2

169 g (1 mol) of phosphorothiochloride are added dropwise over 30 minutes with stirring to a solution of 230 g (1 mol) of 2-methylol tetrahydropyranyl -_ (2) -tetrahydropyranyl- (2 ') - carbinol, 158 g (2 mol) of pyridine and 1000 ecm of benzene while maintaining a temperature the reaction mixture of 40 ° C added. The mixture is then stirred at 25 ° C. for a further 2 hours and left to stand overnight, whereupon filtered and the residue (pyridine hydrochloride) washed with ethyl ether will. The combined filtrates and ether solutions are treated with a concentrated aqueous sodium bicarbonate solution neutralized, washed with 200 ecm of water, dried over calcium sulfate and filtered. The filtrate is purified by distillation up to a bubble temperature of 25 ° C. and less than 2 mm. The residue obtained is purified by mixing with 800 ecm of ethyl ether and filtering. It will be 176 g Spiro - {[2-chloro-2-thiono-4-tetrahydropyranyl- (2 ") -1,3,2-dioxaphosphorinane] -5,2'-tetrahydropyran}

CH ₉

-O XH ₈ -OI

C P-Cl

XH ₂ -CH ₂ CH- · 0 '

, CH - CH ₂ ,
0 CH ₂

CH ₂ - CH ₂

obtain. The properties are as follows: F. 146 to 156 ° C, purity (by esterification) = 97.7%.

P Cl S CH

Found 9.55, 10.26, 10.6, 43.40, 5.96;

calculated .... 9.48, 10.86, 9.81, 44.12, 6.17.

XH ₂ -CH,

The filtrate from the last filtration is obtained by distillation at a pot temperature of 25 ° C at less than 2 mm purified and 108 g of the less pure reaction product are obtained. The residue was a rubbery solid that softened at 70 ° C.

The following diols are examples of further starting materials which can be used in accordance with the process:

2 - methylol - 3,4 - diethyltetrahydropyranyl - (2) - 3 ', 4'-

diethyltetrahydropyranyl- (2 ') -carbinol,
2-methylol-3,3,4,4-tetramethyltetrahydropyranyl- (2) -3 ', 3', 4 ', 4'-tetramethyltetrahydropyranyl- (2') - carbinol,

2-methylol-3,4-di-n-propyltetrahydropyranyl- (2) -3 ', 4'-

di-n-propyltetrahydropyranyl- (2 ') - carbinol,
2-methylol-3,4-di-n-butyltetrahydropyranyl- (2) -3 ', 4'-di-n-butyltetrahydropyranyl- (2') - carbinol,
2-methylol-3,4-di-n-hexyltetrahydropyranyl- (2) -3 ', 4'-

di-n-nexyltetrahydropyranyl- (2 ') - carbinol,
2-methylol-3,4-di-n-pentyltetrahydropyranyl- (2) -3 ', 4'-

di-n-pentyltetrahydropyranyl- (2 ') - carbinol,
2-methylol-3,4-di-n-undecyltetrahydropyranyl- (2) -7 "3 ', 4'-di-n-undecyltetrahydropyranyl- (2') - carbinol,

2-methylol-3,4-di- (l "-ethylpropyl) -tetrahydropyranyl- (2) -3 ', 4'-di- (Ι' '- ethylpropyl) -tetrahydropyranyl- (2') - carbinol,

2-methylol-3,4-di- (Ι "- ethylpentyl) - tetrahydropyranyl - (2) - 3 ', 4'-di - (I "-äthylpentyli-tetrahydropyranyl- (2') - carbinol,

2 - methylol - 3,3,4,4 - tetra - η - butyltetrahydropyranyl- (2) -S '^'. ^ '- tetra-n-butyltetraliydropyranyl- (2') - carbinol,

2-methylol-3,3,4,4-tetra-n-hexyltetrahydropyranyl- (2) -S '^' ^ '^' - tetra-n-hexyltetrahydropyranyl- (2 ') - carbinol,

2-methylol-3,3,4,4-tetra- (2 "-ethylhexyl) -tetrahydropyranyl- (2) -3 ', 3', 4 ', 4'-tetra- (2" -ethylhexyl) -tetrahydropyranyl- (2 ') - carbinol.

The spirophosphoric acid ester halides prepared according to the invention and spirothiophosphoric acid ester halides are useful as pesticides.

Thus, the compound according to Example 1 is an effective ao insecticide which causes 90 to 100% killing of red spider mites when it is used in concentrations of only 30 mg / 100 ecm aqueous solution, and which is 90 to 100% causes 100 ° / ₀ cent kill of bean aphids in 24 hours when it is 100 cc of aqueous solution is used in concentrations of 15 mg / ml. The compound according to Example 2 is very effective for 90 to 100 ° / ₀ sodium destruction of Mexican bean beetle larvae in 72 hours when she / 100 cc of aqueous solution is used in concentrations as low as 7.5 mg.

The procedural products can also be used as intermediate products serve to produce new phosphoric acid esters.

Claims (1)

Claim ·. Process for the preparation of spirophosphoric acid ester halides and spirothiophosphoric acid ester halides by reacting phosphorus oxychloride or bromide in the presence of an inert organic solvent at a temperature between 10 and 40 ° C or phosphorothiochloride or bromide in the presence of an inert organic solvent and a hydrogen halide binder at a temperature between 25 and 60 ° C with diols, characterized in that the phosphorus oxychloride or bromide or phosphorothiochloride or bromide with diols of the general formula Z 'C CH, O H ¹ CHOH in Z a tetrahydropyranyl- (2) -, 3,4-dialkyl- or 3,3,4,4-tetraalkyltetrahydropyranyl- (2) -, tetrahydropyranyl- (3) -, 2,4-dialkyl- or 2,2 , 4,4-tetraalkyltetrahydropyranyl- (3) radical and Z 'represents a -CRR'-CRR'-CH ₂ -CH ₂ -O- or CRR' - O - CH ₂ -CH ₂ - CRR 'radical, in which R and R 'denote hydrogen atoms or alkyl groups, to form spiro compounds of the general formula ! Z 'C CH ₂ -O. X 'CH-O' Ρ —Hal in which X represents an oxygen or sulfur atom and Hai represents a chlorine or bromine atom. © 909 759/423 J.