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Publication numberUS3687952 A
Publication typeGrant
Publication date29 Aug 1972
Filing date19 Feb 1969
Priority date31 May 1968
Publication numberUS 3687952 A, US 3687952A, US-A-3687952, US3687952 A, US3687952A
InventorsRoshdy Ismail
Original AssigneeDynamit Nobel Ag
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
HALOGENPHENOXY-s-TRIAZINE DERIVATIVES HAVING IMPROVED SOLUBILITY
US 3687952 A
Abstract
Novel halophenoxy-s-triazine derivatives and salts thereof characterized by improved solubilities having the formula:
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United States Patent Ismail Aug. 29, 1972 [54] HALOGENPHENOXY-S-TRIAZINE thereof characterized by improved solubilities having DERIVATIVES HAVING IMPROVED the formula:- SOLUBILITY 1 1 N [72] inventor: Roshdy Ismail, Rodderstrasse 6,

5213 Spich, Germany 1 [73] Assignee: Dynamit Nobel Aktiengesellschaft, I X \C/ X Troisdorf, Germany iii '1 d: F b. 19 l [22] e e 969 wherein X represents from one to five halogen atoms PP 800,699 and R is either of [30] Foreign Application Priority Data Feb. 21, 1968 Germany ..P 17 70 591.2 "fly May 31, 1968 Germany ..P 17 70 549.6

52 U.S. Cl. ..260/248 cs, 260/249.5, 260/999 wherein R2 is alkyl h1ving five carbm mm, [51] Int Cl and 55/50 halogenated alkyl having one to five carbon atoms, al-

I kali metal or onium, 3 is y g alkyl having [58] Field of Search ..260/248 CS, 249.5 two to '18 halogenated alkyl having two to 18 carbon atoms or cycloalkyl, and R is alkyl, [56] References Cited cycloalkyl, aryl, halogenated alkyl, halogenated UNITED STATES PATENTS cycloalkyl or halogenated aryl, and wherein R and R taken together with the nitrogen atom to which they 2 5 3: 31 121 21356 are attached form a heterocyclic ring.

Primary Examiner-John M. Ford Att0meyBurgess, Dinklage & Sprung [57] ABSTRACT Novel halophenoxy-s-triazine derivatives and salts The novel triazine derivatives and their salts are suita ble for use as water repellants, parting agents, textile adjuvants, as fire retardants, fungicidal, phytotoxic,

bactericidal and insecticidal agents.

10 Claims, No Drawings HALOGENPHENOXY-S-TRIAZINE DERIVATIVES Where, in the above set out formula R is HAVING IMPROVED SOLUBILITY This invention relates to halogenphenoxy-s-triazine derivatives having improved solubility characteristics.

According to the present invention there is provided a novel group of halogenphenoxy-s-triazine derivatives which have the formula:-

wherein X represents from one halogen or an amino group of the formula:-

in which R represents alkyl, halogenated alkyl, alkali metal, or ammonium, R represents hydrogen, alkyl containing two to 18 carbon atoms, halogenated alkyl containing two to 18 carbon atoms or cycloalkyl and R represents alkyl, containing two to 18 carbon atoms, halogenated alkyl containing two to 18 carbon atoms, cycloalkyl or aryl and wherein R and R taken together can form a heterocyclic ring.

The novel derivatives of the invention are characterized in that they are soluble in organic solvents. The highly chlorinated halogenphenoxy-s-triazines which have heretofore been available and particularly those containing the pentachlorophenoxy group, exhibit only a very slight solubility in organic solvents.

In accordance with the invention it has been found that the solubility in organic solvents is considerably improved by replacing the halogen atoms in carbonhalogenated halogenphenoxy-s-triazines, i.e., those which still contain reactive halogen atoms, with the above-defined moiety R Thus for example, 2-chloro- 4,6-di-(pentachlorophenoxy)-s-triazine, which has a melting point of 327 C is substantially insoluble in nearly all organic solvents, while 2-phosphonic acid diethylester4,6-di-(pentachlorophenoxy)-s-triazine is readily soluble in aromatic and chlorinated hydrocarbons. This can be seen from the following Table. The compatibility of the triazine compounds with aromatic solvents is of great importance in practice.

Comparison of solubility in various organic solvents at 25C of compounds a and b in grams per 100 milliliters.

the preparation of the new triazine compounds is carried out by reacting a halogenphenoxy-s-triazine with a phosphorus acid ester at a temperature between 50 C. and 250 C and preferably at a temperature of from C to 200 C. The re-esterification can be carried out both in the fused state and with an organic solvent. The reaction temperature is increased as the reaction proceeds so that the reaction mixture is constantly boiling. Alkyl halide is split off in the reaction, and the course of the reaction can be followed on the basis of the quantity of alkyl halide that is recovered. The reaction generally requires from 1 to 6 hours. After the evolution of alkyl halide has ended, the unreacted reactants are separated off by vacuum distillation. In most instances the distillation residue is analytically pure and requires no further purification measures.

Aliphatic and aromatic hydrocarbons as well as simple and cyclic ethers are suitable as solvents for use in the reaction. It is advantageous to use not only the solvents in pure form, as for example, an aliphatic hydrocarbon compound such as isoctane, but also their mixtures can be used, such as benzine fractions, instance fractions having a boiling range of from to 200 C.

Chlorinated hydrocarbons such as dichlorothane, tetrachlorethylene, and pentachlorethane, can also be used as solvents. Benzene, toluene, o-dichlorbenzene and xylene are examples of suitable aromatic hydrocarbons. Instances of suitable ethers include: diisopropyl ether, diisoamyl ether, diphenyl ether, 1,4-dioxane etc. The above enumeration is indicative of the fact that both aliphatic and aromatic open-chain ethers can be satisfactorily used. Polar solvents such as dimethylsulfoxide, dimethylformamide, the dimethyl ether of diethylene glycol, and decaline, have also been found to be useful as solvents.

The starting materials for use in the process of the invention can be halogenated phenoxy-triazine derivatives containing reactive chlorine atoms, such as have been described in US. Pat. application Ser. No. 737129, now abandoned.

The phosphorus acid esters which can be used in the reaction with the triazine derivatives include the trialkyl phosphites in general. Lower alkyl esters of phosphorus acid, such as triethyl phosphite, tripropyl phosphite, etc., are preferred for the reaction. Halogenated trialkylphosphites, such as tris-(B- chlorethyl)-phosphite can also be advantageously used in the reaction according to the invention.

The saponification of these phosphonic acid ester derivatives with alkali to thereby form the alkali salts of phosphonic acid increases the solubility of the resulting compounds in water.

The saponification to form the salts is carried out by conventional methods, as for instance, by dissolving the phosphonic acid ester derivatives in organic solvents and heating them with an alkali.

The organic solvents which can be used for dissolv- 5 ing the phosphonic acid ester derivatives include alcohols and ketones, as for example ethanol, acetone etc., as well as the solvents mentioned heretofore in connection with the reaction of the halogenphenoxy-striazines with alkyl phosphites.

The preparation of the compounds of the invention in which R represents an amino radical, is carried out by reacting a C-chloride of a halogenated phenoxy-striazine, in the presence of a tertiary amine or of an acid amide as catalyst, at a temperature between 50 C and 250 C and preferably 80 C to 200 C, with an amine of the formula:

HWN

wherein R and R have the same significances as given above. The reaction can be conducted either with the reactants in the fused state or in an inert solvent. The inert solvent then having the function both of a genuine solvent and of a dispersing agent. The solvents which have been enumerated as suitable for use in the reaction of the halogenphenoxy-s-triazine with phosphorus acid esters can also be used for the reaction with the amine Ra H--N/ .34.

The catalysts for use in the reaction are tertiary amines having aliphatic, cycloaliphatic and aromatic radicals in which case the substituted imines are to be understood as constituting a type of cyclic tertiary amine.

Other catalysts which may be used are acid amides or N-mono or disubstituted acid amides of monobasic, aliphatic, aromatic or araliphatic carboxylic acids having one to 18 carbon atoms. These acid amides have been described for instance in US. Pat. application Ser. No. 737,129, now abandoned.

To some extent, however, the amines used for the reaction themselves serve as reaction catalysts, so that the use of a special catalyst of the kind described above can in many instances be dispensed with.

The new compounds and their salts can be used as water repellants, parting agents, dressings for glass fabrics, textile adjuvants, for the surface treatment of various materials and articles because of their fire-retardant, fungicidal, phytotoxic, bactericidal and insecticidal properties. They can also be used as additives for varnishes and enamels.

The following Examples are given for the purpose of more clearly illustrating the invention and are not to be construed as limiting.

EXAMPLE 1 2phosphonic acid diethy1ester,6-di-(trichlorophenoxy)-triazine 50.7 g of 2-chloro-4,6-di-(trichlorophenoxy)-striazine and 18.6 ml of triethylphosphite were weighed out and placed in a 250 ml 4-necked flask equipped with a stirrer, condenser, thermometer and a nitrogen gas introducing tube. The reaction mixture was slowly heated to 155 C and stirred for 2 hours at this temperature while being maintained under a current of nitrogen. The mixture was thereafter cooled to 120 C and the excess triethylphosphite removed by distillation in vacuo. The recovered product had a melting point of 74-78 C.

EXAMPLE 2 diethylester-4,6-di-( pen- Analysis Found Calculated C 31.67 30.60 H 1.51 1.34 N 5.83 5.63 CI 47.10 47.55 F 4.30 4.16

The sodium salt of this compound was prepared as follows: 8 grams of the substance were dissolved in ml of acetone and then added under stirring to a sodium hydroxide solution in water (lgram/S ml H O). After 30 minutes stirring, the solution mixture was evaporated.

EXAMPLE 3 2-[phosphonic acid di-(B-chlorethyD-ester]-4,6-di- (tetrachlorophenoxy)-triazine There were introduced into a 100 ml 4-neck flask provided with stirrer, condenser, thermometer, and nitrogen gas introduction tube, 28.8 g of 2-ch1oro-4,6- di-(tetrachloro-phenoxy)-s-triazine and 13.5 g of tris- B-chlorethylphosphite. While maintained under a current of nitrogen gas, the reaction mixture was slowly heated to 200 C and stirred at this temperature for 2 hours. The recovered product had a melting point of l l l-1 14 C.

Analysis Found Calculated C 3 1 .40 3 1 .20 1-1 1 .35 1 .37 N 5.63 5.67 CI 48.46 48.60 P 4.40 4.20

EXAMPLE 4 2-anilide,4,6di(2,4,6-trichlorophenoxy)-s-triazine 18.4 g of cyanuric chloride, 39.5 g of 2,4,6- trichlorophenol and 0.5 m1 of dimethylcyclohexylamine were introduced into a three-necked flask provided with stirrer, condenser and introduction tube and ml of xylene then added. The mixture was stirred at the boiling temperature of the xylene, and the HCl gas which evolved was flushed out of the reaction mixture with nitrogen gas and trapped in caustic soda solution. After approximately 66% HO had been split off, 9.3 g of aniline were added to the reaction mixture. The reaction was completed after a period of about 29 hours. The precipitate which developed was filtered and dried. The melting point of the product was 186-l88 C.

EXAMPLE 5 2-anilide, 4,6-di-(pentachlorophenoxy)-s-triazine A product having a melting point of 207-209 C was obtained.

In a three-necked flask provided with stirrer, con- EXAMPLE9 denser and introduction tube, 18.4 g of cyanuric 5 chloride, 53.3 g of pentachlorophenol and 0.5 ml of 2'd1'(g'eihylhexyhmmo)'46'dl'(pentachlorophenoxy)-s-tr1az1ne qulnohne were comblned 1n 120 ml of xylene. The rrux- Th d f E l d d ture was stirred at the boilin tem erature of thex lene e proce ure xam? e were repeate an d h HC] h d p fl h d y 19.34 g of 2-chloro-4,6-d1-(pentachlorophenoxy)-san e gas evo ve was e out of the triazine were reacted with 7.18 g of di-(2-ethylhexreaction mixture wlth N and entrapped in NaOI-I solu- 10 ylamine) and Xylene as solvem tiOn. After had been Off, g Of aniline A product was btained having a point of were added to the mixture. Following a period of about 107 11() C, 19 hours, the reaction was completed. The precipitate which was developed was filtered off and dried. M.P. EXAMPLE 10 271-273c.

2-octyl1m1no-4,6-d1-(2,4,6-tr1bromophenoxy)-s- EXAMPLE 6 triazine Using a procedure analogous to that set out in Exam- 2-an1l1de, 4,6-d1-(tr1bromophenoxy)-s-tr1az1ne ple 6, 2225 g of 2 chloro 4,6 di (2,4,6 In a three-necked flask prov1ded=w1th stirrer, con- 20 tribromophenoxy) s triazine were reacted with 338 g denser and introductlon tube, 18.4 g of cyanuric f t i ascatalyst and Xylene assolvent, chloride, g Of tribromophenol and ml Of qum- A prgduct having a melting point of 124 128 C was oline were combined and then 120 ml of xylene were bt i d, added thereto. The mixture was stirred at the boiling In like manner, the compounds listed in the Table temperature of the xylene and the HCl gas which was which follows were prepared.

Elemental analysis Theory Found Plwuoxy-S-triazine Ep., Yiold, rh-rivatives E R2 0. percent C H N 01 131" C H N Cl Br 2-octylirhino-4,6-di-(2,4,6-tribron1o H Octyl 124-128 96 31.0 2. 54 6.46 55.4 31.32 2.98 6. 51 54.510

phvnoxy)-striazi11o. 2-(li-(2-0thylhnxylimino)-4,6-di- 2-ethyl- 2'ethyl- 02-05 05 38.08 3.70 5.73 40.15 38.87 3. 08 5.70 40.17

trihron1opl1enoxyl-striazi 110. hexyl hexyl. 2-5111 lhex 11min5-1,0-d1- 2,4,8- H ..d0 190192 02 31.0 2.43 0. 47 55.5 32.48 2. 6.86 55.02

Lribromophenoxy)-s-triazinc. 2-butylimi110-4.fi-di-(2,4,6-t1ib1'omo- H Butyl 207-209 90 28.15 1.73 6.92 50. 25 28.35 1.54 7.22 58.80

phunoxy)striazine. Z-hntylimi110-4,G-di-(pontachloro- H do 247-250 00 33.5 1.47 8.23 52.1 33.05 1.51 8. 00 51.41

phonoxy)-s-t1iazi110. Z-uthylhvxylimino-4,6-di-(pentachloro- H 2-etl1yl- 189-190 99 37.4 2. 44 7.6 48.2 37.91 2. 43 8.22 48.12

plu-noxy)-s-triazinc. hexyl. 2551 7111111liq-4,04114 501055111010 11 P 050 71...- 185-187 05 37.4 2.44 7.6 48.2 37. 87 2.21 8.44 48.5

pllmmxy)-s-triazi110. 2-(11-12+1.hylhvxyliuiino-4fi-di- 20tl1yl- 2-etl1yl- 107-110 05 43.0 3.78 6.6 41.05 44.77 3. 01 7.05 41.03

p0|11110111orophunoxy)-s-tria7in0. hoxyl hexyl.

evolved was flushed out of the reaction mixture with N 1 claim: and trapped in NaOH solution. After 66 percent of HCl 1. A member of the group consisting of compounds had split off, 9.3 g of aniline were added to the reaction 45 having the formula:

mixture. The reaction had ended after about 19 hours. The precipitate which had developed was filtered off and dried. The melting point of the recovered triazine was 220-222 C.

EXAMPLE 7 EXAMPLE 8 2-butylimino-4,6-di-(2,4,6-tribromophenoxy)-striazine By a procedure analogous to that of Example 4, 22.25 g of 2-chloro-4,6-di-(2,4,6-tribromophenoxy)-striazine were reacted with 2.2 g of n-butylamine and xylene as solvent.

wherein X represents from one to five chlorine atoms, and R represents a member selected from the group of wherein R represents a member of the group consisting of alkyl having one to five carbon atoms,- halogenated alkyl having one to five carbon atoms, alkali metal and ammonium, R is hydrogen or a two to 18 carbon atom member selected from the group consisting of alkyl, cycloalkyl and haloalkyl, and R is a two to 18 carbon atom member selected from the group consisting of alkyl, cycloalkyl, haloalkyl and carbocyclic aryl, wherein R and R taken together are alkylene and taken together with the nitrogen atom to which they are attached can also form a cycloalkylimino ring having no more than six carbon atoms,

6. A compound according to claim 1 designated 2- I anilide, 4,6-di-(pentachlorophenoxy)-s-triazine.

"7. A compound according to claim 1 designated 2- anilide, 4,6-di-(tribromophenoxy )-s-triazine.

8. A compound according to claim 1 designated 2- (2-ethylhexylimino)-4,6-di-(2,3,4,6- tetrachlorophenoxy)-s-triazine.

9. A compound according to claim 1 designated 2- butylimino-4,6-di-(2,4,6-tribromophenoxy)-s-triazine.

10. A compound according to claim 1 designated 2- di-( 2-ethylhexylimino)-4,6-di-(pentachlorophenoxy)- s-triazine.

Patent Citations
Cited PatentFiling datePublication dateApplicantTitle
US2537816 *9 Jan 1951 Method-of preparing tjnsaturated
US3165513 *26 Dec 196112 Jan 1965Dal Mon Research CoTriazine phosphonium derivatives
Referenced by
Citing PatentFiling datePublication dateApplicantTitle
US4104250 *11 Aug 19761 Aug 1978Borg-Warner CorporationFlame-retardant polymers with 1,3,5-triazines having halo- and halo-aryl substitutents
US5230964 *20 Dec 199027 Jul 1993The Dow Chemical CompanyHigh density recording; durability, wear and friction resistance
US5656701 *8 Nov 199312 Aug 1997Sakata Inx Corp.Polyurethane resins, process for producing the same, and uses thereof
US73451105 Apr 200518 Mar 2008Bayer Materialscience AgProcess for the continuous production of an aqueous polyurethane dispersion
Classifications
U.S. Classification544/211, 987/353, 544/214
International ClassificationC07F9/6521, C08G18/12, C08G18/10
Cooperative ClassificationC08G18/12, C08G18/10, C07F9/65216
European ClassificationC08G18/10, C08G18/12, C07F9/6521K4