N,N'-diphenyl-N-(N"-alkylcarbamoyl)formamidines
关键词
专利信息
专利号 | 3966805 |
已提起 | 02/22/1973 |
专利日期 | 06/28/1976 |
抽象
索偿
What is claimed is:
1. A compound of the formula: ##EQU10## wherein R.sub.1 is hydrogen or alkyl of 1 to 4 carbon atoms,
R.sub.2 is alkyl of 1 to 4 carbon atoms, and either
Ar.sub.1 and Ar.sub.2 are the same, and are each phenyl or a substituted phenyl group selected from ##SPC9##
wherein
R.sub.3 is chlorine, bromine, methyl or methoxy, and
R.sub.4 is chlorine, bromine, methyl, methoxy or trifluoromethyl, or
Ar.sub.2 is phenyl and
Ar.sub.1 is a substituted phenyl group selected from ##SPC10##
wherein
R.sub.3 ' is chlorine or methyl and
R.sub.4 ' is chlorine, methyl or trifluoromethyl,
with the proviso that Ar.sub.1 and Ar.sub.2 are other than ##SPC11##
2. A compound of claim 1, wherein R.sub.1 is hydrogen.
3. The compound of claim 2, which is N,N'-diphenyl-N-(N"-methylcarbamoyl)formamidine.
4. The compound of claim 2, which is N,N'-di-(3-bromophenyl)-N-(N"-methylcarbamoyl)formamidine.
5. The compound of claim 2, which is N,N'-di-(3-trifluoromethylphenyl)-N-(N"-methylcarbamoyl)formamidine.
6. The compound of claim 2, which is N,N'-(4-bromophenyl)-N-(N"-methylcarbamoyl)formamidine.
7. The compound of claim 2, which is N,N'-di-(3-chloro-4-methylphenyl)-N-(N"-methylcarbamoyl)formamidine.
8. The compound of claim 2, which is N,N'-di-(3-chlorophenyl)-N-(N"-methylcarbamoyl)formamidine.
9. The compound of claim 2, which is N,N'-di-(4-methylphenyl)-N-(N"-methylcarbamoyl)formamidine.
10. The compound of claim 2, which is N,N'-di-(3-methoxyphenyl)-N-(N"-methylcarbamoyl)formamidine.
11. The compound of claim 2, which is N,N'-di-(3-methylphenyl)-N-(N"-methylcarbamoyl)formamidine.
12. The compound of claim 2, which is N,N'-di-(3-chloro-4-methoxyphenyl)-N-(N"-methylcarbamoyl)formamidine.
13. The compound of claim 2, which is N-phenyl-N-(N"-methylcarbamoyl)-N'-(4-methylphenyl)formamidine.
14. The compound of claim 2, which is N-phenyl-N-(N"-methylcarbamoyl)-N'-(4-chlorophenyl)formamidine.
15. The compound of claim 2, which is N-phenyl-N-(N"-methylcarbamoyl)-N'-(3,4-dimethylphenyl)formamidine.
16. The compound of claim 2, which is N-phenyl-N-(N"-methylcarbamoyl)-N'-(3,4-dichlorophenyl)formamidine.
17. The compound of claim 2, which is N-phenyl-N-(N"-methylcarbamoyl)-N'-(3-trifluoromethylphenyl)formamidine.
18. A compound of claim 2, wherein R.sub.2 is methyl and Ar.sub.1 and Ar.sub.2 are the same and are each a substituted phenyl group selected from ##SPC12##
19. The compound of claim 18, which is N,N'-di-(4-chlorophenyl)-N-(N"-methylcarbamoyl)formamidine.
20. The compound of claim 18, which is N,N'-di-(3-dichlorophenyl)-N-(N"-methylcarbamoyl)formamidine.
21. A compound of claim 1, wherein R.sub.1 and R.sub.2 are each methyl and Ar.sub.1 and Ar.sub.2 are the same and are each a substituted phenyl group selected from ##SPC13##
wherein R.sub.3 " and R.sub.4 " are each chlorine, bromine or methyl.
22. The compound of claim 21, which is N,N'-di-(4-bromophenyl)-N-(N"-dimethylcarbamoyl)formamidine.
23. The compound of claim 21, which is N,N'-di-(3-chlorophenyl)-N-(N"-dimethylcarbamoyl)formamidine.
24. The compound of claim 21, which is N,N'-di-(4-chlorophenyl)-N-(N"-dimethylcarbamoyl)formamidine.
25. The compound of claim 21, which is N,N-di-(4-methylphenyl)-N-(N"-dimethylcarbamoyl)formamidine.
26. The compound of claim 21, which is N,N'-di-(3-methylphenyl)-N-(N"-dimethylcarbamoyl)formamidine.
27. A compound of claim 1, wherein R.sub.1 is alkyl of 1 to 4 carbon atoms and Ar.sub.1 and Ar.sub.2 are the same and are each phenyl or a substituted phenyl group selected from ##SPC14##
wherein R.sub.3 .sup.IV is chlorine or methoxy and R.sub.4 .sup.IV is chlorine, methoxy or trifluoromethyl.
28. The compound of claim 27, which is N,N'-diphenyl-N-(N"-methylcarbamoyl)formamidine.
29. The compound of claim 27, which is N,N'-di-(3,4-dichlorophenyl)-N-(N"-dimethylcarbamoyl)formamidine.
30. The compound of claim 27, which is N,N'-di-(4-methylphenyl)-N-(N"-dimethylcarbamoyl)formamidine.
31. The compound of claim 27, which is N,N'-di-(3-methoxyphenyl)-N-(N"-dimethylcarbamoyl)formamidine.
32. The compound of claim 27, which is N,N'-di-(3-chloro-4-methoxyphenyl)-N-(N"-dimethylcarbamoyl)formamidine.
33. A compound of claim 1, wherein R.sub.1 is alkyl of 1 to 4 carbon atoms, Ar.sub.2 is phenyl and Ar.sub.1 is a substituted phenyl group selected from ##SPC15##
wherein R.sub.3 .sup.V is chlorine or methyl and R.sub.4 .sup.V is chlorine or methyl.
34. The compound of claim 33, which is N-phenyl-N-(N"-dimethylcarbamoyl)-N'-(3,4-dichlorophenyl)formamidine.
35. The compound of claim 33, which is N-phenyl-N-(N"-dimethylcarbamoyl)-N'-(3,4-dimethylphenyl)formamidine.
36. The compound of claim 33, which is N-phenyl-N-(N"-dimethylcarbamoyl)-N'-(4-chlorophenyl)formamidine.
37. The compound of claim 33, which is N-phenyl-N-(N"-dimethylcarbamoyl)-N'-(4-methylphenyl)formamidine.
描述
Specific Examples of herbicidal compositions will now be described.
Example A
Wettable powder form of composition
25 parts of N,N'-di-(4-chlorophenyl)-N-(N"-dimethylcarbamoyl)formamidine, 5parts of a condensation product from formaldehyde and naphthalene sulphonate, 2 parts of alkyl benzene sulphonate, 5 parts of dextrin, 1 part of ammonium caseinate and 62 parts of diatomaceous earth are mixed until a homogeneous mixture is obtained and then ground until the particles are considerably smaller than 45 microns as an average.
Example B
Wettable powder form of composition
25 parts of N,N'-di-(4-chlorophenyl)-N-(N"-methylcarbamoyl)formamidine, 5 parts of a condensation product from formaldehyde and naphthalene sulphonate, 2 parts of alkyl benzene sulphonate, 5 parts of dextrin, 1 part of ammonium caseinate and 62 parts of diatomaceous earth are mixed until a homogeneous mixture is obtained and then ground until the particles are considerably smaller than 45 microns as an average.
Another aspect of the present invention provides a method of combating weeds in a locus, which comprises applying to the locus a compound of formula I.
the application of the compound may either be pre- or post-emergence of the weeds, and where the locus is a cultivated crop locus and the method is for the selective combating of weeds in the cultivated crop, the compound may be applied either pre- or post-emergence of either the weeds or the crop. Preferably, the compound is applied post-emergence of the crop. The compound may be applied in the form of a herbicidal composition as has been described above.
Specific Examples illustrating the production of compounds of formula I will now be described. Where temperature is referred to, this is in degrees Centigrade.
EXAMPLE 1
N, N'-DI-(4-bromophenyl)-N-(N"-dimethylcarbamoyl)formamidine (process a)
A solution of 35.4 g (0.1 mol) of N,N'-di-(4-bromophenyl) formamidine in 150 cc of hexamethyl phosphoric triamide is added dropwise, at room temperature, to a well stirred suspension of 3.1 g (0.13 mol) of sodium hydride in 100 cc of hexamethyl phosphoric triamide. The mixture is then stirred at room temperature over the course of 2 further hours; subsequently 10.7 (0.1 mol) of dimethylcarbamoyl chloride in 100 cc of hexamethyl phosphoric triamide are added dropwise and the mixture is stirred at room temperature over the course of 12 hours and then cooled in ice. The excess sodium hydride is initially carefully decomposed with a small quantity of water and a total of 2000 cc of water is subsequently added to the reaction mixture, which is extracted twice with 500 cc amounts of benzene. The benzene extracts are dried with potassium carbonate and evaporated. Colourless crystals with a M.P. of 121.degree. are obtained from ether.
Analysis: C.sub.16 H.sub.15 Br.sub.2 N.sub.3 O: Molecular weight: 425.1
Calc. C, 45.2%; H, 3.6%; N, 9.9%; Br 37.6%.
Found: C, 45.7%; H, 3.9%; N, 10.1%; Br, 37.6%.
EXAMPLE 2
N,N'-Di-(3-chlorophenyl)-N-(N"-dimethylcarbamoyl)formamidine (process a)
A solution of 26.5 g (0.1 mol) of N,N'-di-(3chlorophenyl)formamidine in 600 cc of absolute benzene is added dropwise at room temperature to a well stirred suspension of 3.1 g (0.12 mol) of sodium hydride in 100 cc of absolute benzene. The suspension of the resulting sodium salt is subsequently stirred at room temperature over the course of 2 hours. 10.7 g (0.1 mol) of dimethylcarbamoyl chloride in 100 cc of absolute benzene are then added dropwise, the mixture is stirred at room temperature for 12 hours and cooled in ice. The excess of sodium hydride is carefully decomposed with a small quantity of water and a total of 300 cc of water is then added to the reaction mixture. The benzene phase is separated, dried with potassium carbonate and evaporated. Colourless crystals with a M.P. of 111.degree.-112.degree. are obtained from ether.
Analysis: C.sub.16 H.sub.15 Cl.sub.2 N.sub.3 O: Molecular weight: 336.2
Calc. C, 57.6%; H, 4.5%; N, 12.5%; Cl, 21.1%
Found: C, 57.3%; H, 4.6%; N, 12.1%; Cl, 20.7%.
EXAMPLE 3
N,N'-Di-(4-chlorophenyl)-N-N"-methylcarbamoyl)formamidine (process b)
A mixture of 26.5 g (0.1 mol) of N,N'-di-(4-chlorophenyl) formamidine and 11.4 g (0.2 mol) of methyl isocyanate in 150 cc of absolute benzene is heated in a pressure autoclave up to 80.degree. over the course of 60 hours. The autoclave is cooled and opened and the reaction solution is then evaporated down in a rotatory evaporator. The precipitated crystals are suction filtered and washed with petroleum ether. Colourless crystals with a M.P. of 134.degree.-135.degree. are obtained.
Analysis: C.sub.15 H.sub.13 Cl.sub.2 N.sub.3 O: Molecular weight: 322.2
Calc.: C, 55.9%; H, 4.1%; N, 13.0%; Cl, 22.0%.
Found: C, 56.3%; H, 4.1% N, 12.6% Cl, 21.8%.
The compounds of formula I of Examples 4 to 17 are obtained in analogous manner to that described in Examples 1 and 2:
__________________________________________________________________________ ANALYSIS % Exam- Empirical Molecular Calc. ple formula weight M.P. .degree.C Found C H N Cl Br F __________________________________________________________________________ 4 N,N'-Diphenyl-N-(N"-dimethyl- C.sub.16 H.sub.17 N.sub.3 O 267.3 100 71.9 6.4 15.7 carbamoyl)formamidine 72.5 6.8 15.7 5 N,N'-Di-(4-chlorophenyl)-N- C.sub.16 H.sub.15 Cl.sub.2 N.sub.3 O 336.2 124 57.2 4.5 12.5 21.1 (N"-dimethylarbamoyl)for mamidine 57.2 4.4 12.4 21.1 6 N,N'-Di-(3,4-dichlorophenyl)- C.sub.16 H.sub.13 Cl.sub.4 N.sub.3 O 405.1 165 47.5 3.2 10.4 35.0 N-(N"-dimethylcarbamoyl)- 47.7 3.2 10.0 34.9 formamidine 7 N,N'-Di-(3-trifluoromethyl- C.sub.18 H.sub.15 F.sub.6 N.sub.3 O 403.3 syrup 53.7 4.5 10.4 28.2 phenyl)-N-(N"-dimethylcarba- 53.4 3.8 10.9 28.3 moyl)formamidine 8 N,N'-Di-(4-methylphenyl)-N- C.sub.18 H.sub.21 N.sub.3 O 295.4 128-31 73.2 7.2 14.2 (N"-dimethylcarbamoyl)- 72.7 7.1 13.8 formamidine 9 N,N'-Di-(4-bromophenyl)-N- C.sub.16 H.sub.15 Br.sub.2 N.sub.3 O 425.1 121 45.2 3.6 9.9 37.6 (N"-dimethylcarbamoyl)- 45.7 3.9 10.1 37.6 formamidine 10 N,N"-Di-(3-methoxyphenyl)- C.sub.18 H.sub.21 N.sub.3 O.sub.3 327.4 98 66.0 6.5 12.8 N,(N"-dimethylcarbamoyl)- 66.2 6.6 13.2 formamidine 11 N,N'-Di-(3-methylphenyl)- C.sub.18 H.sub.21 N.sub.3 O 295.4 57-58 73.2 7.2 14.2 N-(N"-dimethylcarbamoyl)- 73.2 7.1 14.4 formamidine 12 N,N'-Di-(3-chloro-4-metoxyphe- C.sub.18 H.sub.19 Cl.sub.2 N.sub.3 O.sub.3 396.3 113 54.6 4.8 10.6 17.9 nyl)-N-(N"-dimethylcarbamoyl)- 54.2 4.9 10.4 17.8 formamidine 13 N,N'-Di-(4-diethylsulfonamido- C.sub.20 H.sub.27 N.sub.5 O.sub.5 S.sub.2 481.6 129-30 49.9 5.7 14.5 phenyl)-N-(N"-dimethylcarbamoyl)- 49.9 5.6 14.2 formamidine __________________________________________________________________________
In like manner to the production of the compound of Example 13, the compound N,N'-di-(4-dimethylsulphonamidophenyl)-N-(N"-dimethylcarbamoyl)-f ormamidine is produced.
EXAMPLE 14
N-Phenyl-N-(N"-dimethylcarbamoyl)-N'-(3, 4-dichlorophenyl)formamidine
M.P.: 126.degree.-127.degree.
Analysis: C.sub.16 H.sub.15 Cl.sub.2 N.sub.3 O: Molecular weight: 336.2:
Calc.: C, 57.1%; H, 4.5%; N, 12.5%; Cl, 20.9%.
Found: C, 56.7%; H, 4.5%; N, 12.8%; Cl, 21.5%.
EXAMPLE 15
N-Phenyl-N-(N"-dimethylcarbamoyl)-N'-(3, 4-dimethylphenyl)formamidine
M.P.: 119.degree.-120.degree.
Analysis: C.sub.18 H.sub.21 N.sub.3 O: Molecular weight: 295.4:
Calc.: C, 73.2%; H, 7.2%; N, 14.2%.
Found: C, 73.5%; H, 7.2%; N, 14.2%.
EXAMPLE 16
N-Phenyl-N-(N"-dimethylcarbamoyl)-N'-(4-chlorophenyl)formamidine
M.P.: 112.degree.-115.degree.
Analysis: C.sub.16 H.sub.16 ClN.sub.3 O: Molecular weight: 301.8:
Calc.: C, 63.6%; H, 5.4%; N, 13.9%; Cl, 11.8%.
Found: C, 63.2%; H, 5.3%; N, 13.8%; Cl, 12.8%.
EXAMPLE 17
N-Phenyl-N-(N"-dimethylcarbamoyl)-N'-(4-methylphenyl)formamidine
M.P.: 74.degree.-75.degree.
Analysis: C.sub.17 H.sub.19 N.sub.3 O: Molecular weight: 281.4:
Calc.: C, 72.6%; H, 6.8%; N, 14.9%.
Found: C, 72.2%; H, 6.9%; N, 14.4%.
The compounds of formula I of Examples 18 to 33 may be produced in manner analogous to that described in Examples 1, 2 and 3:
__________________________________________________________________________ ANALYSIS % Exam- Empirical Molecular Calc. ple formula weight M.P. .degree.C Found C H N Cl F Br __________________________________________________________________________ 18 N,N'-Diphenyl-N-(N"-methyl- C.sub.15 H.sub.15 N.sub.3 O 253.1 158-59 71.1 6.0 16.6 carbamoyl)formamidine 71.3 5.9 16.8 19 N,N"-Di-(3,4-dichlorophenyl)- C.sub.15 H.sub.11 Cl.sub.4 N.sub.3 O 391.1 syrup 46.0 2.8 10.7 36.1 N-(N"-methylcarbamoyl)- 47.2 3.4 10.7 35.7 formamidine 20 N,N'-Di-(3-bromophenyl)-N- C.sub.15 H.sub.13 Br.sub.2 N.sub.3 O 411.1 100 43.8 3.2 10.2 38.9 (N"-methylcarbamoyl)formamidine 44.1 3.2 10.1 38.5 21 N,N'-Di-(3-trifluoromethyl- C.sub.13 H.sub.13 F.sub.6 N.sub.3 O 389.3 syrup 52.4 3.4 10.8 29.3 phenyl)-N-(N"-methylcarbamoyl)- 53.1 3.4 10.4 29.8 formamidine 22 N,N'-Di-(4-bromophenyl)-N- C.sub.15 H.sub.13 Br.sub.2 N.sub.3 O 411.1 113-16 43.8 3.2 10.2 38.9 (N"-methylcarbamoyl)- 44.6 3.3 11.2 37.6 formamidine 23 N,N'-Di-(3-chloro-4-methyl- C.sub.17 H.sub.17 Cl.sub.2 N.sub.3 O 350.2 Sirup 58.4 4.9 12.0 20.2 phenyl)-N-(N"-methylcarba- 59.6 5.0 11.6 19.4 moyl)formamidine 24 N,N'-Di-(3-chlorophenyl)-N- C.sub.15 H.sub.13 Cl.sub.2 N.sub.3 O 322.2 100-101 55.9 4.1 13.0 22.0 (N"-methylcarbamoyl)- 56.4 4.0 13.1 21.7 formamidine 25 N,N'-Di-(4-methylphenyl)-N- C.sub.17 H.sub.19 N.sub.3 O 281.3 129-30 72.7 6.8 14.9 (N"-methylcarbamoyl)- 72.6 6.8 14.8 formamidine 26 N,N'-Di-(3-methoxyphenyl)-N- C.sub.17 H.sub.19 N.sub.3 O.sub.3 313.3 138-40 65.2 6.1 13.4 15.3 (N"-methylcarbamoyl)form- 65.2 6.2 13.6 15.4 amidine 27 N,N'-Di-(3-methylphenyl)-N- C.sub.17 H.sub.19 N.sub.3 O 281.3 79-81 72.7 6.8 14.9 (N"-methylcarbamoyl)- 72.6 6.8 14.9 formamidine 28 N,N'-Di-(3-chloro-4-methoxy- C.sub.17 H.sub.17 Cl.sub.2 N.sub.3 O.sub.3 382.2 154-56 53.4 4.5 11.9 18.6 phenyl)-N-(N"-methylcarba- 53.8 4.6 10.0 18.3 moyl)formamidine __________________________________________________________________________
EXAMPLE 29
N-Phenyl-N-(N"-methylcarbamoyl)-N'-(4-methylphenyl)formamidine
M.P.: 122.degree.-124.degree.
Analysis: C.sub.16 H.sub.17 N.sub.3 O: Molecular weight: 267,3: Calc.: C, 71.9%; H, 6.4%; N, 15.7% Found: C, 71.7%; H, 6.4%; N, 15.6%.
EXAMPLE 30
N-Phenyl-N-(N"-methylcarbamoyl)-N'-(4-chlorophenyl)formamidine
M.P.: 120.degree.-121.degree.
Analysis: C.sub.15 H.sub.13 ClN.sub.3 O: Molecular weight: 286.7: Calc.: C, 62.9%; H, 4.6%; N, 14.7%; Cl, 12.4%. Found: C, 62.6%; H, 4.9%; N, 14.2%; Cl, 11.2%.
EXAMPLE 31
N-Phenyl-N-(N"-methylcarbamoyl)-N'-(3,4-dimethylphenyl)formamidine
M.P.: 97.degree.-102.degree.
Analysis: C.sub.17 H.sub.19 N.sub.3 O: Molecular weight: 281.3: Calc.: C, 72.7%; H, 6.8%; N, 14.9%. Found: C, 71.5%; H, 6.9%; N, 15.6%.
EXAMPLE 32
N-Phenyl-N-(N"-methylcarbamoyl)-N'-(3,4-dichlorophenyl)formamidine
M.P.: 107.degree.-111.degree.
Analysis: C.sub.15 H.sub.13 Cl.sub.2 N.sub.3 O: Molecular weight: 322.2. Calc.: C, 56.0% ; H, 4.1% ; N, 13.0% ; Cl, 22.0% . Found: C, 55.7%; H, 4.1%; N, 13.4%; Cl, 22.0%.
EXAMPLE
N-Phenyl-N-(N"-methylcarbamoyl)-N'-(3-trifluoromethylphenyl)formamidine
M.P.: 94.degree.-95.degree.
Analysis: C.sub.16 H.sub.14 F.sub.3 N.sub.3 O: Calc.: C, 59.9%; H, 4.4%; N, 13.1%; F, 17.3%. Found: C, 60.7%; H, 4.5%; N, 13.2%; F, 16.3%.
STARTING MATERIALS
The production of starting materials of formula IIb may be effected in accordance with Example 34 to 48:
EXAMPLE 34
N,N'-Di-(3-chlorophenyl)formamidine
225 g (2 mols) of 3-chloroaniline and 148.2 g (1 mol) of ortho-formic acid triethyl ester are heated in a distillation apparatus up to 100.degree.-150.degree. and the resulting ethyl alcohol is slowly separated by distillation over a Vigreux column. The resulting crude diarylformamidine is recrystallized from ethyl acetate.
M.P.: 113.degree.-114.degree..
Analysis: C.sub.13 H.sub.10 Cl.sub.2 N.sub.2: Molecular weight: 265.2: Calc.: N, 10.5%; Cl, 26.7%. Found: N, 10.5%; Cl, 26.5%.
The compounds of formula IIb of the following Examples 35 to 47 are produced in analogous manner to that described in Example 34.
__________________________________________________________________________ ANALYSIS % Exam- Empirical Molecu- M.P. 0.degree.C Calc. ple R.sub.4 R.sub.3 formula lar Found weight C H N Cl Br __________________________________________________________________________ 35 H Br C.sub.13 H.sub.10 Br.sub.2 N.sub.2 354.1 186-88 44.1 2.8 7.9 45.2 44.3 3.1 7.8 45.0 36 CH.sub.3 CH.sub.3 C.sub.17 H.sub.20 N.sub.2 286.2 134-35 80.9 8.0 11.1 80.7 8.1 10.9 37 H Cl C.sub.13 H.sub.10 Cl.sub.2 N.sub.2 265.2 185 58.9 3.8 10.5 26.7 58.8 3.9 10.7 27.1 38 H OCH.sub.3 C.sub.15 H.sub.16 N.sub.2 O.sub.2 256.3 117-18 70.2 6.3 10.9 70.2 6.2 10.9 39 H SO.sub.2 N(CH.sub.3).sub.2 C.sub.17 H.sub.22 N.sub.4 O.sub.4 S.sub.2 410.5 229-30 49.7 5.4 13.7 49.5 5.3 13.7 40 H CH.sub.3 C.sub.15 H.sub.16 N.sub.2 224.3 140-41 80.4 7.2 12.5 80.3 7.2 12.4 41 Cl CH.sub.3 C.sub.15 H.sub.14 Cl.sub.2 N.sub.2 293.2 157-58 61.5 4.8 9.6 24.1 61.7 4.8 9.5 24.3 42 Cl Cl C.sub.13 H.sub.18 Cl.sub.4 N.sub.2 334.0 158-59 46.8 2.4 8.4 42.4 46.8 2.5 8.3 41.6 43 CH.sub.3 H C.sub.15 H.sub.16 N.sub.2 224.3 123-25 80.4 7.2 12.5 80.2 7.1 12.3 44 OCH.sub.3 H C.sub.15 H.sub.16 N.sub.2 O.sub.2 256.3 109 70.3 6.3 10.9 70.6 6.5 10.9 45 Br H C.sub.13 H.sub.10 Br.sub.2 N.sub.2 354.1 126-27 44.1 2.8 7.9 45.2 44.7 2.8 7.9 44.2 46 Cl OCH.sub.3 C.sub.15 H.sub.14 Cl.sub.2 N.sub.2 O.sub.2 325.2 170-71 55.4 4.3 8.6 21.8 55.5 4.5 9.0 22.3 47 CF.sub.3 H C.sub.15 H.sub.10 F.sub.6 N.sub.2 332.3 121-23 54.2 3.0 8.4 54.2 3.3 8.8 __________________________________________________________________________
EXAMPLE 48
N-Phenyl-N'-(chlorophenyl)formamidine
A mixture of 25.5 g (0.2 mol) of 4-chloroaniline and 29.8 g (0.2 mol) of ethyl-N-phenylformimidate is heated in a distillation apparatus up to 100.degree. over the course of 3 hours and the resulting ethyl alcohol is separated by distillation over a Vigreux column and under slightly reduced pressure (200 torr). The curde diarylformamidine is recrystallized from isopropanol. M.P.: 123.degree.-124.degree..
Analysis: C.sub.13 H.sub.11 ClN.sub.2: Molecular weight: 230.7:
Calc.: C, 67.6%; H, 4.8%; N, 12.1%; Cl, 15.4%. Found: C, 67.8%; H, 4.7%; N, 12.5%; Cl, 15.0%.
The following starting materials of formula IIb are produced in analogous manner to that described in Example 48.
EXAMPLE 49
N-Phenyl-N'-(3,4-dimethylphenyl)formamidine
M.P.: 112.degree.-113.degree.
Analysis: C.sub.15 H.sub.16 N.sub.2: Molecular weight: 224.3: Calc.: C, 80.3%; H, 7.2%; N, 12.5%. Found: C, 80.2%; H, 7.0%; N, 12.7%.
EXAMPLE 50
N-Phenyl-N'-(3-trifluoromethylphenyl)formamidine
M.P.: 112.degree.
Analysis: C.sub.14 H.sub.11 F.sub.3 N.sub.2: Molecular weight: 264.3: Calc.: N, 10.2%; F, 21.6%. Found: N, 10.6%; F, 21.4%.
EXAMPLE 51
(N-Phenyl-N'-(3,4-dichlorophenyl)formamidine
M.P.: 135.degree.
Analysis: C.sub.13 H.sub.10 Cl.sub.2 N.sub.Cl, 26.8%. Molecular weight: 265.1: Calc.: N, 10.6%; Cl, 26.8%. Found: N, 10.6%; Cl, 26.6%.
EXAMPLE 52
(N-Phenyl-N'-(4-methylphenyl)formamidine
M.P.: 95.degree.-97.degree.
Analysis: C.sub.14 H.sub.14 N.sub.2: Molecular weight: 210.3: Calc.: C, 79.8%; H, 6.7%; N, 13.3%. Found: C, 80.0%; H, 6.8%; N, 13.3%.