DE2065977B2 - Process for the preparation of optionally condensed 4,5-bis-trifluoromethylimino-oxazolidines and -imidazolidines - Google Patents

Description

X-H

45

or, if neither X nor Y are oxygen, the group R - N = can also be, where R, R ¹ , R ² , R ³ and R ^{4 are} hydrogen, alkyl, alkenyl and alkynyl with up to 8 carbon atoms, where these groups can be substituted by halogen, cyano, lower alkoxy and alkylmercapto groups, furthermore represent optionally lower alkyl-substituted cycloalkyl, then represent carbalkoxy, furthermore aralkyl with up to 2 carbon atoms in the alkyl part and for aryl with up to 14 Carbon atoms are in the ring system, where the aryl radicals can optionally be substituted by halogen, cyano, nitro, lower alkyl and haloalkyl, lower alkoxy and alkylmercapto, and the radicals R, R ³ and R ⁴ together with R ¹ or R ² for such Can stand radicals which connect Z to X or Y to form a 5- to 7-membered ring which is fused with a benzene ring or partially hydrogenated benzene ring and substituted by halogen, cyano, nitro and lower alkyl can be ert, characterized in that a carbonic acid or carboxylic acid derivative of the general formula II

60 have meaning with perfluoro - 2,5 - diazahexa-2,4-diene of the formula

NCFj

IO

/ V

F NCF ₃

(in)

15th

20 in the presence of a hydrogen fluoride acceptor in the temperature range between -50 and +120 ⁰ C implemented.

2. The method according to claim 1, characterized in that one is used as the hydrogen fluoride acceptor an alkali fluoride is used.

3. Process according to Claims 1 and 2, characterized in that the hydrogen fluoride acceptor is used Sodium fluoride used.

The invention relates to a chemically peculiar process for the preparation of new 4,5-bis-trifluoromethylimino-oxazolidines and imidazolidines.

4,5-bis-trifluoromethylimino derivatives of heterocyclic Rings are not yet known; the substances, the substance class and the manufacturing process are new.

It has been found that the optionally condensed 4,5-bis-trifluoromethylimino-oxazolidines can be used and imidazolidines of the general formula

Z = C

= N-CF ₃

in which X and Y for oxygen, the group

- N -

I.
R ¹

50 or the group

55 - N -
R ²

stand, but X and Y must not stand for oxygen at the same time, and Z for oxygen or the group

R ^s

Z = C (II) C =

\ 65 /

YH R ⁴

in which the radicals X, Y and Z are as mentioned above, or if neither X nor Y are oxygen.

can also denote the group R — N =, where R, R ¹ , R ² , R ³ and R ⁴ stand for hydrogen, alkyl, alkenyl and alkynyl with up to 8 carbon atoms, these groups being represented by halogen, cyano, lower alkoxy and alkyl mercapto groups can be substituted, further represent optionally lower alkyl-substituted cycloalkyl, then represent carbalkoxy, further represent aralkyl with up to 2 carbon atoms in the alkyl part and aryl with up to 14 carbon atoms in the ring system, the aryl radicals optionally can be substituted by halogen, cyano, nitro, lower alkyl and haloalkyl, lower alkoxy and alkyl mercapto, furthermore the radicals R, R ³ and R ⁴ together with R ¹ or R ² can be those radicals which Z with X or Y below Connect formation of a 5- to 7-ring, which can be condensed with a benzene ring or partially hydrogenated benzene ring and substituted by halogen, cyano, nitro and lower alkyl, by reacting carbonic acid or. Carboxylic acid derivatives of the general formula

Z = C

X-H

Y- ¹ -H

(II)

Have meaning with perfluoro-2,5-diazahexa-2,4-diene the formula

15th

in which X, Y and Z are those given above

F N-CF ₃

\ Z c

c / V

F N-CF ₃

(III)

in the presence of a hydrogen fluoride acceptor in the temperature range between -50 and + 120 ° C.

It can be described as surprising that the abovementioned compounds of the formula (II) with Pcrfluor-2, f - Diazahexa -2,4-diene of the formula (III) in more uniform Reaction gives the previously unknown five-membered rings of the formula (I) with a satisfactory yield. if Perfluoro-2,5-diazahexa-2,4-diene is also formally a derivative of oxalic acid, so the person skilled in the art could do not expect the claimed reaction to proceed smoothly since it was known that the perfluor-2,5-diazahexa-2,4-diene tends to self-condensation under the reaction conditions used (cf. J. Am. Chem. Soc. 89, 5010 [1967]).

Using N, N'-dimethylurea and perfluoro-2,5-diazahexa-2,4-diene as starting materials and sodium fluoride as the acid binding agent, the The reaction sequence can be represented by the following equation:

CH ₃

NH F N-CF ₃

O = C + f + 2NaF - O = C

\ Λ

NH F N-CF ₃ - ¹

CH,

NJ = N-CF ₃

+ 2NaHF ₂
= N-CF ₃

CH ₃

CH ₃

If 3-Methyi-pyrazolon- (5) is used, the course of the reaction can be given by the following formula Enol form reacts, and perfluoro-2,5-diazahexa-scheme are reproduced: 2,4-diene as starting materials in addition to sodium fluoride, so 45

N-CF ₃

^H ~ | NH
H ₃ CV /

H
H ₃ C

OH
NH

N-CF ₃ + 2NaF

N-CF ₃

+ 2NaHF _{2 N} / ^ N-CF ₃

The carbons X and Y to be used as starting materials preferably represent oxygen, the group acid or carboxylic acid derivatives are through the

The above formula (II) is generally defined. In this formula —N -

Z sees preferably oxygen, the group I.

RN =, if neither X nor Y are oxygen, 60 R ¹

and for the group

and the group

R ³

65 N.
R ²

R ⁴

however, X and Y do not represent oxygen at the same time

are allowed to stand and where the radicals R, R ¹ , R ² , R ³ and R ⁴ preferably represent hydrogen, alkyl and alkenyl with up to 6 carbon atoms each, the latter two groups preferably being represented by fluorine, chlorine, bromine, cyano and / or lower alkyl mercaptos as can be substituted by lower alkoxy groups, furthermore preferably for cyclopentyl and cyclohexyl, for carbomethoxy and carboethoxy, further preferably for benzyl, for aryl with up to carbon atoms in the ring system, the aromatic rings preferably being fluorine, chlorine, bromine , Cyano, nitro, methyl, ethyl, isopropyl, chloromethyl, trifluoromethyl, methoxy and methyl mercapto can be substituted, also preferably for those radicals which can connect Z to X and Y to form a 5- to 6-membered ring.

The conlene acid and carboxylic acid derivatives of the general to be used as starting materials Most of the formula (II) are known and can be represented in a manner which is generally known; you get it z. B. if you have carbonated or Reacts carboxylic acid halides with ammonia or amines; furthermore, many are under the general formula (II) falling urea derivatives can be prepared in a known manner from primary amines and isocyanates, For example, the following isocyanates may be mentioned:

p-trifluoromethyl-phenyl isocyanate, p-nitrophenyl isocyanate.

Methyl isocyanate,

Isopropyl isocyanate,

t-butyl isocyanate,

Cyclohexyl isocyanate,

Allyl isocyanate,

/ i-chloroethyl isocyanate,

Phenyl isocyanate,

o-nitrophenyl isocyanate,

p-nitrophenyl isocyanate,

m-nitrophenyl isocyanate,

o-chloro-phenyl isocyanate,

m-chloro-phenyl isocyanate,

3,4-dichlorophenyl isocyanate,

p-chloro-phenyl isocyanate,

/ i-naphthyl isocyanate,

Benzyl isocyanate,

Stearyl isocyanate,

/ i-cyano-ethyl isocyanate,

Ethyl isocyanate,

n-propyl isocyanate,

n-butyl isocyanate,

'sobutylisocyamt,

2-ethyl-hexyl isocyanate,

p-methoxyphenyl isocyanate,

p-methyl mercaptophyl isocyanate,

Methoxy ethyl isocyanate, "

(-.- Cyanopentyl isocyanate.

Examples of primary amines include the amines on which the isocyanates mentioned are based The following amines are also suitable for the preparation of compounds of the formula (II):

2-amino-1-methyl-cyclohexane, 2-chloro-aniline,

3-nitroaniline,

2-chloro-4-nitro-aniline,

5-chloro-2-arr, ', no-toluene,

4-chloro-3-amino-benzotrifluoride.

30th

35

40

45

50 1-amino-2-phenylethane, 2-amino-1-isopropylbenzene, 5-amino-l, 2,4-trimethylbenzene, 5,6,7,8-tetrahydronaphthalene- (1), 3,5-dichloroaniline, 2 , 4,5-trichloraniline, 2,4-dichloroaniline, 2,3-dichloroaniline, 2,5-dichloroaniline, 3-chloroaniline,

4-chloroaniline,

4-chloro-2-nitroaniline, aniline,

2-nitroaniline,

4-nitroanine,

S-chloro ^ -nitroaniline, 4-chloro-3-nitroaniline, S-ChloM-nitroaniline, 4,6-dichloro-2-nitroariiline, 2,5-dichloro-4-nitroariiline.

2, o-dichloro-4-nitroaniin.

2-amino-toluene, 3-chloro-2-aminotoluene, 4-chloro-2-amino-toluene, S-nitro ^ -amino-l ^ -dimethyl-benzene, o-Nitro ^ -amino-l ^ -dimethyl-benzene.

5-amino-5-amino
2-amino-2-amino-6-amino-2-amino

, 3-dimethyl-benzene,

, 3-bis-trifluoromethyl-benzene.

, 4-dimethylbenzrl,

-methyl-3-ethylbenzene,

, 2,4-trimethyl-benzene.

, 3,5-trimethyl-benzene,

2-amino-1,3-diethyl benzene, 4-Amino-1, S-dimethyl-S-ethyl-benzene.

4-Amino-1-methyl-3,5-diet 1-benzene.

2-amino-1,3-diisopropylbenzene, 5,6,7,8-tetrahydronaphthalene- (2), / i-bromo-ethylamine, 1-cyano-1-phenyl-ethylamine, 1-cyano-1-methyl-ethylamine , 5-chloro-2-amino-benzotrifluoride, 6-chloro-2-amino-toluene, 4,5-dichloro-2-amino-toluene !, 3-nitro-2-amino-toluene, 4-nitro-2- amino-toluene, 5-nitro-2-amino-toluene, 6-nitro-2-amino-toluene, 4-chloro-5-nitro-2-amino-toluene, 3-amino-toluene, 4-chloro-3- aminotoluene, o-chloro-i-aminotoluene, 4,6-dichloro-3-aminotoluene, 4-aminotoluene, 2-chloro-4-aminotoluene, 2-nitro- ^{i <} -amino -toluene, 3-nitro-4-aminotoluene, 2-amino-1-ethylbenzene, 1-amino-1-phenylethane.

2,3-Dirr.v-thylaniline, 2,6-dimethylaniline, 3,4-dimethylaniline, 2,4-dimethylaniline.

The guanidines falling under the formula (II), such as. B. 2-aminijbenzimidazole, 2- [amino- (carbomethoxy)] - benzimidazole, ρ - chlorophenylimido - N, N '- diethylurea are available in a manner known from the literature.

The l'crfluor-2.4-dia / ahexa-2.4-diene used as the starting material the formula (III) is known (.1. Am. (hem. Soe. X9. 5007 [I9r, 7ji.

All inert organic solvents can be used as diluents. These preferably include Hydrocarbons, such as gasoline: also benzene. Toluene: Nil rile, such as acetonitrile: chlorinated Hydrocarbons such as B. Met hy leneh I orid. chloroform and chlorobenzene.

All common acid binders can be used as acid binders be used. Alkali carbonates can be mentioned. Alkali bicarbonates, tertiary amines, like triethylamine. Dimethylaniline As in practice Hydrogen acceptors to be used with preference In particular, the alkali fluorides have proven to be useful, with nairium fluoride in particular.

The reaction temperatures can be varied between -50 and 4120.degree. Preferably works between -30 and +90 C

To carry out the method according to the invention one sets I mol of the compound of the formula (II) I mol of perfluoro-2.5-diazahexa-2.4-diene Formula (III). the alkali fluoride is seeded in excess (about 3 to 4 mol), but under or The specified proportions are exceeded made by up to 20 percent by weight without significantly lowering the yield will. Expediently, the perfluoro-2.5-dkizahexa-2.4-diene is left to a suspension consisting of starting material, organic solvent and Hydrogen acceptor. drops. Then filtered one away from fluoride. constricts and recrystallizes. Another way of working up is that one water is added to the reaction salt and the resulting residue is optionally recrystallized.

The compounds obtainable by the process according to the invention are highly fungitoxic Effect on. They have a broad spectrum of activity and can be used against parasitic ones Fungi that attack above-ground parts of plants or attack the plants from the ground as well against seed-borne pathogens.

The compounds which can be prepared according to the process also have an insecticidal and acaricidal active wedge. The products are used with success in crop protection to combat harmful sucking and sucking biting insects, dipteras and mites (acarina) as well as in the veterinary and hygiene sector, furthermore Used in the protection of stored products against a large number of animal pests (endo- and eIctoparasites).

Examples of implementation
example 1

CH ₃

O = C

fluorine-2.5-dia / .ahexa-2.4-dicn was added dropwise. One lets about Follow up for 30 minutes under reflux, filtered from sodium hydrogen fluoride and sodium fluoride and the filtrate is concentrated in vacuo. After recrystallization from ether pentane, 19 g of 1,3-diynethyl-4.5 are obtained - bis - (rifluoromethylimino - imidazolon - (2) with a melting point of 109 MOC. The current time is (> ') "" Eier theory.

Example 2
Il

CH ₃

23 g (0.1 mol) of per- CH ₂ C are added to 9 g (0.1 mol!) Of N, N'-dinsethylurea and 15 g (0.36 mol) of sodium fluoride in 150 ml of benzene at a temperature of 50.degree

N ι NCF,

O NCF ",

Analogously to Example I, the above compound is obtained with acetamide instead of N, N'-dimethyl urea. Of the Melting point (from ether pentane) is 90 92 C (with decomposition). Mass spectrum: 247 mc. The yield is 30%, of theory.

Example 3

H, C ■ - ■ · - N

N -v N (T,

O - ^J NCF,

23 g are added to 10 g (0.1 mol) of 3-methylpyrazolone (5) and 15 g of sodium fluoride in KXImI acetonitrile (0.1 mol) perfluoro-2.5-diazahcxa-2.4-diene was added dropwise at a temperature of -30 C. Leave for 2 hours stir at 0 C, filtered from sodium hydrogen fluoride and sodium fluoride and concentrated Filtrate in vacuo. After recrystallization from ether hexane, the compound formulated above is obtained of m.p. 95-96 "C. Mass spectrum: 286 me. Yield: 45% of theory.

Example 4
CH.,

NJ = NCF ₃

O = C

VL

NCF ₃

Analogously to Example 1, with Np-Chlorophenyl-N'-meihylharnsloiT siatt N, N'-Dimethyiharnstoff the above formulated compound, mp 172-173 ⁰ C. Yield:. 92% of theory.

Il c i s ρ i e I 5 (Ή,

15 ο ι s ρ i c 1 9

Cl

O C

N ■ NC [·,

N! NCK,

NfF-,

C ₂ II ₅ NC

Analogously to example I one obtains with N-I'henyl-N-melhy I urea instead of N. N'-liimel hy! Urea the above formulated connection from ip. 159 160 C. Yield: 89 "π of theory.

F) e i s ρ i e I 6

Il

O C

NC'F-,

NCI,

. Analog Example 3 is obtained with N-phenyl urea instead of 3-methyl-pyrazolone- (5) the compound formulated above with melting point 162 163 C. bulge: 55 "ο

the theory. _n . . , _

Example 7

CH,

O -C

N-pNCF,

N- ^ NCF ₃

Analogously to Example 1, N-cyclohexal-N'-methylurea is obtained the compound formulated above with a melting point of 135-136 = C. Yield: 70% of theory.

Example 8 CH ₃

N 'NCI-',
C ₂ FI ₅

Analogously to Example 3, p-chlorophenylimido-N.N'-diethylurea is obtained the above compound of IP: 95 96 C. Yield: 69% of theory.

Example 10

-N

I!

'■' ■ N N-COCH ₁

i {

F ₃ CN NCF,

Analogously to Example 3, 2- [amino- (carbomethoxy)] -benzimidazole is obtained the above compound of m.p. 152 153 C (from acetone). Yield: 74% of the Theory.

Example Il

/ Vn

~ ^y N NH

J-L

F ₁ CN NCF,

Analogously to Example 3, 2-amino-benzimidazole is obtained the above compound has a melting point of> 175 "C. (with decomposition). Yield: 70% of theory.

T = NCF ₃

, Ν—,

O = C

I = NCF ₃

N-t = NCF ₃

O = C

NCF ₃

Analogously to Example I are obtained with N-3,4-Dichior- phenyl-N'-methylharnstoffdie above compound from the Fd: 149-150 ⁰ C. Yield: 84% of theory.

Analogously to Example 1, the above compound is obtained with N- (3-chloro-4-tri nuormethyi) -pheriy'i-N'-meihyihurea with a melting point of 95-96 ° C. Yield: 75% of theory.

il

H e i s ρ i

12th

13th

N; ■ - N

O -C

N Cl-,

Analogously to Example I, with N.N'-DiphenylhaniMoff, the above-formulated compound of melting point l ^l ) 7 to I ') X Γ Aiwhpnlf. ·· 70% iji.-r theory is obtained

Example 14

C) -C

No ι κ- . "H- CH, Ip.
I Cl \ llvhowl
1 "., Il. Lh.I 16 CMI ₅ 161 77 17th C ₁ I l CH, - OCH, 13X 75 IX I- I ₅ -CN 130 72 1 <) C ₄ H ,, -ClI, / S 145 7X 20th iC ₄ ! l " 135 76 21 1-C ₄ Il ₁ , 143 147 70 22nd CH, C 136 Ύ) 23 H IXI 74 24 CH, - 143 74 I ₂ I. 94 Xl 26th CH, 133 73

N- - ι

--N-CF,

N N --I = N CF,

Furthermore, the following compounds represented by the general formula were also similarly made

CF., -N N CF,

Analogously to Example 3, ethyl 2-pyridinecarbamate is obtained the compound formulated above with a melting point of 150 C (decomp.). Yield: 73% of the j-, Theory.

Example 15

N NC-OCH ₅

J-I

F ₁ CN N-CF,

Analogously to Example 3, 2- [amino (carboethoxy)] benzimidazole is obtained the above compound of m.p. 108'C (decomp.). Yield: 76% of theory.

The following compounds of the general formula were also used in a corresponding manner

CF ₃ -N N-CF ₃

ν ^ -NN-R O

; ,, --- N N-CH ₃

Ύ ^

from connections of the type

■ \) - NH - CO - NH - C H., A.

CF ₁ -N = CF-CF = N-CF ₃

55

from the connections of the type

/ ~ V-NH-CO-NH-R ² and

60

65

CF ₃ -JN = CF-CF = N-CF ₃

manufactured:

manufactured: 2-CI Example Λ,
No. 3-Cl 27 3-Cl, 5-Cl 28 2-CH ₃ 29 J- ^ n ₃ 30th 4-CH ₃ 3! 4-C ₂ H ₅ 32 3-OC ₂ H ₅ 33 4-OC ₂ H ₅ 34 3-CH ₃ , 4-CH ₃ 35 2-CI, 4-Cl 36 2-CH ₃ , 6-CH ₃ 37 2-C ₂ H ₅ , 6-C ₂ H ₅ 38 39

Kp.
(Cl Howl
ΓΌ d. Th. 102-104 69 131 78 167 75 116 72 i27 S3 116 81 114 79 115 74 148 74 I08-1IO 75 122 68 138 70 107 69

13th

14th

■ ortsct / img \., I Cl \ llslVllk '
{"" .1 Wed ι Hispid
Ni 2-C) CH, 107 73 40 2-CH ,. 3-CH, 120 74 41 2-iC, H ₇ 82-86 71 42 2-CII ,. 4-CH.,. 5-CH, 150 70 43 3-C) CH, 116 118 75 44 I,. 4-CI 148 72 ι 45

Similarly, the following can also be used Compounds of the general formula

Cl-, N N-Cl-,

■ j Λ ,,

NN CH, CH ₂ OCH,

C)

The following compounds of the general formula were also shown

... CF ₁ -N N-CF,

Cl-

from connections of the type

NII ■■ < ^X :>

ro A _n

NH CH, CII, -OCH ₁ and

CF., N Cl- Cl- "N CF, are produced:

N NR-

cl \.,

from connections of the type
Cl

Cl> NH-CC) -NH- W

licisptcl
Sr. R- 46 C ₂ H ₅ 47 QH ₇ 48 i-QH ₇ 49 C ₄ H,

Cl · "., - N-CF CF N -CF-" ,:

Ip.
I Cl

• \ u-bi

r "d.

IHC

Th.I

124-126 76

114-117 77

114-117 71

120-122 80

102-105 78

89-95 71 -CH ₂ -CH ₂ -OCH ₃ 76-78 74 were also prepared:

54 55 56 57 58 59 60 61 62 63 64 65

Ip. \., Six-nk

I Cl I .. il lh. ι

2-CI. 4-CI 2-CH, 4-OC ₂ H ₅ 4-CH, 3-CH, 4-CI penta Cl 2-iC, H-2-CH ,. 4-CH, 2-CH ,. 3-CH, 2-C ₃ H ₅ 3-Cl, 4-CH, 7-QH ₅ . 6-C ₂ H ₅ . 3-CL 4-Ci, 5-CI 2-OCHj. 4-CI, 5-CH, 2-OC H, 3-OCH ₁ 3-OCH ₃ . 4-CH, 3-CN 3-NO ₂

115 113 121 118 107 122

69

72 81 79 75 71

I08-M1

74-76

115-118

88-92

74-76

97-9 '

84-85

101-102

71-73

108-1Ii

115-117

120-121

125-127

Example formula No.

CF ₃

CH ₂ -CH ₂ -NN-

N N-

N N-

-CF ₃ -CH ₃

Fp. Γ C)

93

Dent (% of theory)

75

15th 20 65 977 Fp CF ₃ -N N-CF ₃ H CF ₃ -N N-CF ₃ 16 Dent c continuation I Ο // - ^ -N N-CO-OCH ₃ 174-175
N-CO-OCH ₃ H (% d.Th Example Knrmcl 73 {y the following compounds of the general formula were also used R ¹ -NN-R ² yield 62 No Y 1% of the total 71 NO 61 R ¹ R ² 66 65 / ^ S-CH ₂ CO-OCH ₃ Then R. CH ₃ - O ^^ V - CO-OCH ₃ Cl CO-OCH ₃ Cl - <^ ~~ V- CO-OCH ₃ CO-OCH ₃ O CO-OCH ₃ obtain Fp. example I C) No. 122-123 74 190 (decomp.) 75 157 (decomp.) 76 157 77

Claims (1)

Patent claims: 1. Process for the preparation of optionally condensed 4,5-bis-trifluoromethyliminooxazolidines and imidazolidines of the general formula I. Z == C = N-CF ₃ (I) in which X and Y for oxygen, the group
—N— R ¹
or the group - N -
R ² stand, but X and Y must not stand for oxygen at the same time, and Z for oxygen or the group R ³ R ⁴ C = J