Process for preparing heterocyclic compounds

专利摘要:
A compound of the formula <IMAGE> wherein typical representations of X, Y and Z is oxygen or sulfur; R1 is methyl; R2 is phenyl substituted with chlor, methyl, methoxy, nitro or methylenedioxy; and R3 is cyclohexyl, methylcyclohexyl or tetrahydropyranyl, is useful as an acaricide.
公开号:SU1075974A3
申请号:SU823381349
申请日:1982-01-28
公开日:1984-02-23
发明作者:Иватаки Исао；Каерияма Минору；Мацуи Нобуо；Ямада Томио
申请人:Ниппон Сода Компани,Лимитед (Фирма)；
IPC主号:

专利说明:

cycloalkyl, 2-methylcyclohexyl, 3-methylcyclghexyl, 4-methylcyclohexyl, β-dimethylcyclohexyl, chichexenyl, 2-tetrahydropyranyl, 4-tetrahydro-othiopyranyl, 1,4-dioxanyl-2, N-methyl-piperidinyl-4 or 2-3-a-3-a-a-3-a-a-3-a-a-3-a-a-a-a-overl-1-methyl; ;
At and Z - independently from each other oxygen or sulfur.
one
This invention relates to methods for the preparation of new heterocyclic compounds of general formula I 1H.-K-SSH-Kz g-N CHHTGl JOL Pg X t (Go) Rfx (7 where X, y and Z are independently of each other oxygen or sulfur; R. - alkyl containing 1 to 3 carbon atoms; R, FURIL, thienyl, feil substituted phenyl having one or two substituents selected from alkyl, halogen, halomethyl, methoxy, nitroyl methylenedioxy radical R - five, six, or seven-membered cycloalkyl, 2-methylcyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 2 6-dimethylcyclohexyl, cyclohexenyl, 2-tetrahydropy anil, 4-tetrahydrothiopyranyl, 1,4-dioxanil-2, Nm tylpiperidinyl-4 or 2-methyl-1,4-dihydrooxothianil-3, which have acaricidal activity and can be used in agriculture. (no formula
which is that oxa; ZOLIDIN-2-OH is reacted with a compound of the formula in an organic solvent medium in the presence of a base as a catalyst at room temperature. The compound of formula II has a relaxing, laxative effect of Cl. It is known to use in agriculture N, H-dimethyl-and- (2-methyl-4chglorfe NJL) formanidine (chlordimeform) of the formula) 2 as an acericidal preparation t2. The aim of the invention is the synthesis of new heterocyclic compounds that can be used in agriculture as acaricides. This objective is achieved by a process for the preparation of compounds of the general formula I, namely, that the compound of the general formula ItfiCZBDRj RZ C№-KI, where. X, Z, R, A, R-, and k, have the indicated meanings, are reacted with trichloro lethylchloroformate or thio1) osgen in the medium of an organic solvent in the presence of the acid c1 acceptor.
Example 1. trans-3-Cyclohexylcarbamoyl-4-methyl-5- (4-methylphenyl) -2-oxazolidone.
In 100 ml of ethyl acetate are dissolved 2 g of l-cyclohexyl-3-fl-oxy-l- (4 methylphenyl) 2-propyl urea and 1.6 g of H, H-dimethylaylin, and the solution is added with stirring at 1 p trichloromethyl chloroformate dissolved in 10 ml of ethyl acetate. After the mixture was stirred for one hour at this temperature, the reaction mixture was washed with hydrochloric acid and water, the washed mixture was dried and the solvent was evaporated. The yield of the target product is 1.7 g.
Example 2. trans-4-methyl-5- (4-methylphenyl) -3- (2-tetrahydropyranylcarbamoyl) -oxa olidi n-2-thione. 1.2 g of 1- (2-tetrahydropyranyl) -3- {threo-2-hydroxy-1- (4-methylphenyl) -2propyl urea and 1.0 g of I, N-dimethylaniline are dissolved in 10 MP of ethyl acetate. , and to the solution of 11 add. with stirring at 0 ° C, 0.7 g of thiophosgene dissolved in 5 ml of ethyl acetate. After stirring the mixture for 3 hours, the reaction mixture is poured into 5% hydrochloric acid and extracted with ethyl acetate. The ethyl acetate layer was dried, the solvent was evaporated, and the oily residue was purified by column chromatography. The yield of the target product is 0, 5 g.
I Example 3 trans-4-Methl-5 (4-methylphenyl) -3-qi clrhexylcarba moyl-2-thiazolidone.
4.8 g of 1-cyclohexyl-3-threo-1-mercapto-1- (4-methylphenyl) -2-propyl urea and 3.8 g of H, H-dimethylaniline are dissolved in 50 ml of ethyl acetate,
5 and to the solution, with stirring, 2.5 g of trichloromethyl chloroformate dissolved in 1 ml of ethyl acetate are added. After stirring the mixture for 4 hours at room temperature, the reaction mixture was washed with 5% hydrochloric acid and water, and the washed mixture was dried and the solvent was evaporated. The oily residue is purified by column chromatography. Output
5 of the target product is 3.4 g. The phyico-chemical characteristics of the compounds of general formula I are given in table. one. . It a b l and c a -1
Oh CH,
Oh oh
CH,
ABOUT
nt 1.5330
64-65J
four
CH,
five
CH,
CH,
85-86,5J C129-130J
G105-107
CH.
80-82J
Continued table. one
O.CH34O
ОНз: Г112-и8 (н / СНу trance)
Continued table. one
eleven
m 3
OOOCHj
About Oh, DOS
OOOSN
OOOCHj
OOOCHj
SOOCHj
SOOCHj
SOOSN
SOOSN
SOOCHj
SOOCHj
SOOCH
S00CHj
SOOCHj
SOOSN
8OOSN
OOSN,
.
1 1 I 3 I
continuation of the table. f
7
OH,
Och-,
S
oh,
eight
ABOUT
Оt) CH,
S
S
about sn0
S
Ghi
ABOUT
72
SO
OCHA
CH,
72
Och,
74
about sn.
75s
about sn.
76
about sn.
77S
aboutCHs
78
ABOUT
about CH79S
about sn.
Sn,
about
80- S
nJ4,5751

108-110
ci
15
- 1 2 1L
 S 81 82E 83S 84 85E 86 87S OCH, 88B OCH89S OCH, 90S 91S 92S oCjH oCH, .93S 94S oCHj osn 95S 96S oCHj 97S oCHj oCH, 98 "S
sixteen
Continued table. 1 i. I
Jl
1 l 116-121 .5: trans). H C83-87: cis) eHj | l49-153: trsh1s) -Q: n5 1.5801 O ° p) H p, 1.5604 N tl06-108j N) G97-98 N) 87-89J 120-121j Yau 95-91 II LI ll3-115 / 120-123 LZ S83-85, 5679 xr. 67-68 / | l33-137j
Prev Table one
Och,
99S
100s
CH,
ABOUT
101S
Och,
ABOUT
OS, N
102
3
103 s
About CH
CH,
104
about
CH,
105 O
Configuration of the isomer in the carbineoyl group.
The proposed compounds exhibit significant acaricidal properties, they are particularly useful for fighting the eggs and larvae of acarids. Among acarids, which can be effectively stratified using the proposed compounds, spider mite spider mite, citrus red mite, etc. The compounds can be successfully used to control ticks. In addition, a herbicidal effect can be expected for some group of compounds.
The proposed compounds are used, if desired, in the form of conventional acaricidal compositions with conventional diluents or excipients. Formulations include wettable powders, granules, pulverulent powders, emulsifiable concentrates, flowable formulations, and the like. .
The use of combinations of the proposed compound with other plant protection products, for example, other acaricides, insecticides or herbicides, can give acaricidal and insecticidal compositions having efficacy unattainable for individual KOMnoHeHTqB compositions.
The other components with which the proposed compounds can be used are, for example, acaricides: chlorophenetol, chlorobenzylate, chloropropyl, proclonol, phenizobromolate, dicofol, dynobathon, vinapacryl, chlimeimeform, amitraz, propargite, PPPPS, benzoxam ancholc, and benzoxamc, anhydropholcadecaphenolcaphenolcaphenolcaphenolcaphenolcaphenolcaphenolcanecaphenolcane, chlorophenol, chloridimeform, amitraz, propargite. thiocainox, chlorophenones, tetradifon, tetrasul, cycloprate, Kai cide, Kai ho, 3-n-dodecyl-1, 4-naphthoquinone-2-ylacetate, calcium polysulfide; insecticides; propoxur; pyrethroids: permethrin, cypermethrin, decamethrin, fenvalerate, fenpropathrin. pyrethrin, allethrins, tetramethrin, resmethrin, bartrin, dimethrin, propatrine, prothrin, 3-phenoxybenzyl-2, 2-dichloro-1- (4-ethoxyphenyl) 1-cyclopropanecarboxylate, o6-cyano-3-phenoxybenzyl-2, 2-dichloro -1- (4-ethoxyphenyl -1-cyclopropanecarboxylate, (RS; -o. Iano-3-phenoxybenzyl (RS) -2- (4-trichloromethoxyphenyl) -3-methylbugilate, (CB) -ob-cyano-3-phenoxybenzyl (RS) -2- (2-chloro-4-trichloromethylanilino) 3-methylbutylate.
Significant activity of the proposed compounds can be seen from the following tests.
Primary leaves of haricot, planted in pots, were infected by 30 adult females of arachnoid, two-bedded. The leaves were sprayed until a water droplet appeared with an aqueous emulsion prepared from an emulsion concentrate and containing 500 ppm or 125 ppm of active compound. Three days after the laying period, the surviving mites, as well as those killed, were collected from the leaves. On the 11th day determined
damage rate as a percentage
AB from, where A is the number of ticks that developed from the eggs on the untreated leaves; B is the number of ticks developed from the eggs on the treated leaves. Results are shown in abl. 2
Cha & Face
211075974
Continued table. 2
22
Continued Tab. 2

权利要求:
Claims (4)
[1]
METHOD FOR PRODUCING HETEROCYCLIC COMPOUNDS of the general formula where X, Y and Ζ are independently oxygen or sulfur;
R, is alkyl containing 1-3 carbon atoms;
R. - furyl, thienyl, phenyl, substituted phenyl having one or two substituents selected from’ alkyl, halogen, halogen methyl, methixyl, nitro or methylenedioxy;
R- - five-, six- or seven-membered cycloalkyl,
[2]
2-methylcyclohexyl,
[3]
3- methylcyclohexyl,
[4]
4- methylcyclohexyl ^
2,6-dimethylcyclohexyl, cyclohexenyl,
2-tetrahydropyranyl,
4-tetrahydrothiopyrapyl,
1,4-dioxanyl-2, N-methylpiperidinyl-4 or 2-methyl-1,4-dihydrooxothianyl-3, characterized in that the compound of the general formula
HHCZNHRi I ^s
Vl CH ~ Rt G / ¹ sn-khn where X, Z, r ₁₉ and Rj have the indicated values, they are reacted with trichloromethylchloroformate or thiophosgene in an organic solvent in the presence of an acid acceptor. Priority according to criteria;
SU ... 1075974 A • · "
10/03/79 at R ^ - methyl;
R ₂ is phenyl substituted with methyl;
R is cyclohexyl; X ³ oxygen;
Z is oxygen, Y is oxygen;
04/18/80 when R ^ - alkyl containing 1-3 carbon atoms;
R ^ ”FUR ^IL " thienyl, phenyl, substituted phenylimine one or two substituents selected from alkyl, halogen, halomethyl, methoxy, nitro or methylenedioxy groups;
R, - five-, six- or seven-membered cycloalkyl, 2 • methylcyclohexyl, 3-methylcyclohexyl, 4-methylcyclo- ¹ Loghexyl, 2,6-dimethylcyclohexyl, cyclohexenyl, 2-tetrahydro-tyranyl, 4-tetrahydro Othiopyranyl, 1,4-dioxanyl-2, N-methylpiperidinyl 4 or 2-methyl-1,4-dihydrooxothianyl-3;
X, Y and Z are independently oxygen or sulfur.

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引用文献:

---

公开号 | 申请日 | 公开日 | 申请人 | 专利标题

---

---

US3193559A|1965-07-06|New derivatives of z-oxazolidinones |

---

US3119833A|1961-12-01|1964-01-28|Dow Chemical Co|2-oxazolidinone 3-carbanilides|

---

US3491108A|1967-09-18|1970-01-20|Olin Mathieson|5,5-dialkyl-substituted 1,3-thiazolidin-2-ones|

---

BE763964A|1970-03-24|1971-09-08|Delalande Sa|NEW DERIVATIVES OF AMINOCARBONYL-3 OXAZOLIDINONE-2, THEIR METHOD OF PREPARATION AND THEIR APPLICATION IN THERAPEUTICS|

---

FR2249656B1|1973-11-07|1977-04-15|Delalande Sa|

---

DE2655369A1|1976-12-03|1978-06-08|Schering Ag|5- -OXAZOLIDINONE AND THEIR SULFUR ANALOGS AND PROCESS FOR THEIR PRODUCTION|

---

IL61016A|1979-10-03|1984-02-29|Nippon Soda Co|3-carboxamidederivatives of oxazolidine and thiazolidine-2-one,their preparation and acaricidal compositions containing them|

---

JP4811018B2|2005-12-28|2011-11-09|Ｊｆｅスチール株式会社|Deoxidation method for molten steel|IL61016A|1979-10-03|1984-02-29|Nippon Soda Co|3-carboxamidederivatives of oxazolidine and thiazolidine-2-one,their preparation and acaricidal compositions containing them|

---

JPH0755937B2|1986-07-29|1995-06-14|日本曹達株式会社|Oxazolidine derivative, its production method and acaricide|

---

US4971959A|1987-04-14|1990-11-20|Warner-Lambert Company|Trisubstituted phenyl analogs having activity for congestive heart failure|

---

US5274002A|1987-04-14|1993-12-28|Warner-Lambert Company|Trisubstituted phenyl analogs having activity for congestive heart failure|

---

FR2631029B2|1987-05-14|1991-04-05|Cortial|NOVEL ARYLCARBAMOYL-3 AMINOMETHYL-5 OXAZOLIDINES AND THEIR SALTS WITH PHARMACOLOGICALLY COMPATIBLE ACIDS|

---

FR2615190B1|1987-05-14|1989-07-21|Cortial|NOVEL ARYLCARBAMOYL-3 AMINOMETHYL-5 OXAZOLIDINES AS WELL AS THEIR SALTS WITH PHARMACEUTICALLY COMPATIBLE ACIDS, THEIR PREPARATION METHOD AND THEIR PHARMACEUTICAL APPLICATION|

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法律状态:

优先权:

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申请号 | 申请日 | 专利标题

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JP54127707A|JPS6320230B2|1979-10-03|1979-10-03|

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JP5036380A|JPH0215545B2|1980-04-18|1980-04-18|

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