RU1775400C - Process for production of 3-endohalogen-7,7-bis(trifluoromethyl) -1-asatricyclo-[2,2,1,o@@@]-heptanes - Google Patents

Abstract

SUMMARY OF THE INVENTION: product 3-endo-halogen-7,7-bis (trifluoromethyl) -1-azatricyclo [2.2.1.0 ^ '^] phosphol ICh2-sn2-sn-sn-sn5 ^ NJQlFjC- C-CF where Hal- [, Vgili C1. Reagent 1: 3,3-bis trifluoromethyl) -2-azabicyclo [2.2.2] gent-5-ene. Reagent 2: N-halogen-pyridinium halide. Ru Br 2, Ru? Cl or alkyl hypochlorite (tert. BuOCI). Process conditions: in an aprotic solvent. Used as spectrum pesticides.

Description

The invention relates to an improved process for the preparation of 3-endogalogen-7, 7-bis (trifluoromethyl) -1-azatricyclo 2, 2,1,0 heptanes, which can be used as broad spectrum pesticides.

A known two-stage method for producing 3-endo-bromo-7,7-bis (trifluoromethyl) 1-azatricyclo 2, 2,1,0 heptane, based on the addition of bromine to 3,3bis (trifluoromethyl) -2-azabicyclo 2,2,1 hept-5-enu with the formation of 6,7-dibromo-3,3bis (trifluoromethyl) -2-azabicyclo 2.2.1 heptane and its subsequent cyclization by dehydrobromination with potassium tert-butylate.

A disadvantage of the known method is its low processability - it is carried out in two stages, involves the isolation of an intermediate compound and the use of hard-to-reach potassium tert-butylate, as well as a low total yield of the target compound (up to 27%). The method has limited use, since it allows to obtain only a single representative in the series of 3-endo-halogen-1-azatrices 1 cl 2,2,2,0 J. heptanes, namely bromine-containing.

The aim of the invention is to simplify the process, increase yield and expand the range of target compounds.

To achieve this goal in the method for producing 3-endo-halogen-7,7bis (trifluoromethyl) -1-azatricyclo 2.2.1.0 heptanes of the general formula I

where Hal II, Br. C1

by reacting 3,3-bis (trifluoromethyl) -2-azabicyclo 2.2.1 hept-5-ene with ha / 1ogen-dehydrohalogenating

agent according to the invention, as

which uses alkyl hypochlorite

(tert-BuOCI) or N-halo-pyridinium halide of formula II

RU. Hal2 (ll), where NaB Br2, let,

and the process is carried out in an aprotic solvent, followed by isolation of the desired product by fractional distillation in vacuo.

A comparative analysis of this method with the prototype shows that the method differs from the known one in that it is carried out in one step by reacting 3,3-bis (trifluoromethyl) -2azabicyclo 2, 2,1 hept-5-ene with N-halogen-pyridinium halidomide

alkyl hypochlorite.

Using this method, it is possible to obtain, with a yield of 61-75.5%, various halogen derivatives of 1-azatricyclo 2.2.1.0 heptanes, increase the yield of bromine-produced tricyclane 2.5 times in comparison with the prototype.

The composition and structure of the obtained compounds are proved by elemental analysis, IR spectra, and NMR spectra. The compounds are storage stable under normal conditions (physical properties and spectrometric data remain unchanged for 3 months or more). The compounds are poorly soluble in water, well soluble in alcohols, acetonitrile, acetone, polyhaloalkanes, benzene and other common organic solvents.

The invention is illustrated by examples.

Example 1. Obtaining 3-endo-bromo-7,7bis (trifluoromethyl) -1-azabicyclo 2.2.1.0: heptane.

To a solution of 2.3 g (0.01 M) 3,3-bis (trifluoromethyl) -2-azabicyclo 2.2.1 hept-5-ene in 10 ml of chloromethylmethylene, 2.4 g (0, OR) were added with stirring ) Ru-Vga in 10 ml of methylene chloride for 0.5 hour. Then the solution was stirred for another 1 hour, washed with water (ml) and dried over CaCla. Subsequent distillation under reduced pressure yielded 2.02 g (65%) of a colorless substance with a boiling point. 75 ° C at 10 mm Hg. Art., 1.4 300, 1.804.

Found,%: С30.97: Н 1.79,4,59,24,49.

Calculated,%: C 30.97, H 1.93, 4.52. 25.80.

IR spectrum in CCI4. cm 3085 o.sl, 3040 o. at., 2995 about. el., 29300. el., 1473 about. sp., 1350 s, 1295 s, 1277 s, 1243 sp., 1237 sp. 1227 Wed, 1211 about. S., 1185s, 1170sr, 1165 sp .. 1153 sp., 1125 sp., 1071 sp., YubGer .. 1036 sp., 1023 sp., 1010 sp., 973 sp., 947 sp., 840 sp., 460 about. el., NMRN, 50% in ecu, TMS, ppm: 2.5k AB

(5-H, 2H, I 12 Hz), 2.85 s (4-H. 1H), 2.95 s (2-H and 6-H: 2H), 4.75 s (3-H, 1H) )

, 50% in CCI4, CFCI3, ppm; 63, OM (2СРз).

Example 2. Obtaining 3-endo-iodine-7,7bie (trifluoromethyl) -1-azabicyclo 2.2.1.0 heptane. To a mixture of 5.0 g (0.02 m) of Ru | a solution of 4.6 (0.02 m) of 3,3-bis (trifluoromethyl) -2-azabicyclo 2, 2,1 hept-5- was added in 25 ml of acetonitrile ene in 10 ml of acetonitrile. After stirring for 2 hours, 50 ml of NaO was added. The lower layer was separated, dissolved in 10 ml of CH2CI2, and washed with 25 ml of 20% NaaSaOs solution. After

dried over CaCl2, distillation under reduced pressure yielded 4.3 g (61%) of the acetone substance with bp. 45-47 at 0.5 mmHg. st., 1.4654,, 2.00.

Found,%: C 27.74; H 1.37.4.94.35.39.

CsHeNiFe.

Calculated,%; C 26.89: H 1.68, 3.92, 35.55.

IR spectrum, in CCI4, em; 3080 o.s., 3036 o.s., 2970 o.s., 2925 o.s.,, 1478s., 1338s.,

1303 p. 1293 s, 1272 s, 1251 s, 1227 s, 1208 O.S. .. 1282s, 1162 sr., 1144 sr., 1127 sp., 1072 sr., 1060 sr., 1035s, 1023s, 1010 sr., 973 sr ., 946 Wed, 911 about. el., 835 Wed, 813 Wed, 130 Wed, 723 Wed, 692 about, el., 543 about. .el., 446 about. at., 414

o.sl.

NMRN, TMS, 50% in ecu, M.D .; 2.43 s (5-H, 2H), 2.83 (4-H, 1 H), 2.97 s and 3.0 s (2-H and 6-H.2H).

, CGC13, 50% in CCU: 63 m. AzVz

(2CF3).

Example 3. Obtaining 3-endo-chloro-7,7bie (trifluoromethyl) -1-azatricyclo 2.2.1, heptane. To a solution of 4.6 g (0.02 m) of 3,3-bis (trifluoromethyl) -1-azatricyclo 2.2.1 -hept-5-ene

10 ml of acetonitrile at 90 ° C added a solution of 3.0 g (0.028 m) of tert-butyl hypochlorite in 10 ml of acetonitrile for 1 h, after which the mixture was heated at 90 ° C for another 0.5 h. Subsequent distillation under reduced

4.0 g (75.5%) of a colorless substance, i.e., boiling, were isolated under pressure. 65-66 ° at 10 mmHg. et., 1.4150, 1.575.

Found,%: C 37.20; H, 2.12; 5.45. C 13.47.

CsHeNFeCI.

Calculated,%: C 36.16; H 2.26, 5.27, 13.37. .

Claims (1)

IR spectrum in ecu, 1085 sp., 3040 about. e., 2995 about. el., 2930 el., 1475 about. el., 1377 el., 1313 er., 1222 e, 1263 e, 1237, 1212 about. el., 1200 e, 1187 e, 1167 o. at., 1137 about. eat .. 1140 eat., 11230 about. at., 1067 about. el., 1058 el., 1033 er., 2019 er., 1009 about. el., 968 el., 941 o., el., 924 o. at., 9080 about. at., 853 er. NMR H, 50% in CCI4, TMS. M.D .: 2.45 K, AB (5-H, 2H, 12 Hz). 2.75 s (4-H. H-1), 2.85 s (2-Ni6-H, 2H), 4.7s (3-H, 1H). . 50% in CCI4. СРС1з, ppm, б4м, AzVz (2СРз). An advantage of this method is the ability to produce the desired compounds in a single step. This makes it possible to simplify the hardware design of the process, to reduce by 2-3 times the labor costs and the time required for synthesis. Compared to the prototype, the method is more accessible since, in contrast to the prototype, hard-to-reach potassium tpeT-butylate is not used. Compared with the prototype, the method allows a 2.5-fold increase in the yield of the bromine derivative of tricyclane and makes it possible to obtain, with a rather high yield, new 3-znodohalogen (iodine, chlorine) -7.7-bis (trifluoromethyl) -1-azatricyclo-2 2.1.0 heptanes. SUMMARY OF THE INVENTION Method for the preparation of 3-znodo-halogen-7.7bis (trifluoromethyl) -1-azatricyclo 2,2,1,0 heptanes of the general formula CP 3 where Hal is an atom of iodine, bromine or chlorine 3,3-bis (trifluoromethyl-1-azatricyclic , 2.1, () T hbp-5-ene is reacted with a halogenating agent, which is different) And, in order to simplify the process, increase the yield and expand the range of target products, N-halogen-pyridinium halide of the formula is used as a halogenating agent. where Hal is 812 or | C1, or alkylginochlorite (tert. BuOCI), and the process is carried out in an aprotic solvent, followed by isolation of the desired product by fractional distillation in vacuo.