LT3286B - Method for the preparation of acylaminobenzamides derivatives - Google Patents

Method for the preparation of acylaminobenzamides derivatives Download PDF

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LT3286B
LT3286B LTIP578A LTIP578A LT3286B LT 3286 B LT3286 B LT 3286B LT IP578 A LTIP578 A LT IP578A LT IP578 A LTIP578 A LT IP578A LT 3286 B LT3286 B LT 3286B
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alkyl
chloro
compounds
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compound
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Patrick Jeff Crowley
Rosamund Alison Lansdown
Alasdair Thomas Glen
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Ici Plc
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    • C07D295/16—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms acylated on ring nitrogen atoms
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Description

Šis išradimas skirtas naujiems fungicidiniams acilamino-benzamidams ir jų gavimo būdui.The present invention relates to novel fungicidal acylamino-benzamides and processes for their preparation.

Būtina nurodyti Anglijos paraišką Nr. 42454/77 patentui gauti, kuria remiantis buvo gautas JAV patentas Nr. 4282218 ir EP-A-0127990. Pirmojoje aprašomi acilanilidai, pasižymintys antiandrogeninėmis savybėmis, o vėlesniame - anilino dariniai, pasižymintys fungicidinėmis savybėmis.English Application No. U.S. Patent No. 4,2454/77, on the basis of which U.S. Pat. 4282218 and EP-A-0127990. The first describes the anti-androgenic properties of acylanilides, and the subsequent one describes the fungicidal properties of the aniline derivatives.

Šiame išradime siūlomi junginiai, kurių formulė (I):The present invention provides compounds of formula (I):

kurioje A ir B nepriklausomai yra H, fluoras, chloras, bromas, alkilas, alkoksilas arba halogen {Cr.Ą) alkilas, su sąlyga, jei A ir B vienu metu nėra H; D ir E nepriklausomai yra H arba fluoras; R1 yra H, C1_4alkilas arba C1.4alkoksilas; R2 yra C1_4alkilas, C1_4alkoksilas arba pasirinktinai pakeistas fenilas, arba R1 ir R2 kartu su azoto atomu, prie kurio jie prijungti, sudaro morfolino, piperidino arba azetidino žiedą, pasirinktinai pakeistą alkilu; R3 yra H; R4 yra trichlormetilas, C2_8alkilas (pasirinktinai pakeistas halogenu, C._8alkoksilo arba R1S(O)n grupe, kur R1 yra Cr_4 alkilas, C2 4 alkenilas arba C2_4 alkinilas, o n yra 0, 1 arba 2), ciklopropilas (pasirinktinai pakeistas halogenu arba C1.4alkilu) , C2-8 alkenilas, C2.8 alkinilas, C2_8 alkoksilu, mono- arba di (C2_4) alkilamino arba R’’ON=C(CN) grupė, kur R'' yra Ο4_4 alkilas, arbawherein A and B are independently H, fluorine, chlorine, bromine, alkyl, alkoxyl or halogen {C r . (A ) alkyl, provided A and B are not simultaneously H; D and E are independently H or fluoro; R 1 is H, C 1-4 alkyl or C 1-4 alkoxyl; R 2 is C1_ 4 alkyl, C 1 _ 4 alkoxy, or optionally substituted phenyl, or R 1 and R 2 together with the nitrogen atom to which they are attached form a morpholino, piperidino or an azetidine ring optionally substituted with alkyl; R 3 is H; R 4 is trichloromethyl, C 2 _ 8 alkyl (optionally substituted with halogen, C._ 8 alkoxy or R 1 S (O) n group, wherein R 1 is CR_ I 4 alkyl, C 2 4 alkenyl or C 2 _ 4 alkinyl, on is 0, 1 or 2), cyclopropyl (optionally substituted with halogen or C first 4 alkyl), C 2-8 alkenyl, C 2nd 8 alkynyl, C 2 _ 8 alkoxy, mono- or di (C 2 _ 4) alkylamino or R''ON = C (CN) group, wherein R "is Ο 4 _ 4 alkyl, or

R ir R kartu su C(O)N grupe, prie kurios jie prijungti sudaro azetidin-2-ono žiedą, pasirinktinai pakeistą halogenu arba Cx.4 alkilu; ir X ir Y nepriklausomai yra deguonis arba siera.R and R together with the C (O) N group to which they are attached form an azetidin-2-one ring optionally substituted with halogen or C x . 4 alkyl; and X and Y are independently oxygen or sulfur.

Alkilo grupės ir kitų alkilą turinčių grupių liekanos gali būti linijinės arba šakotos. Tai, pavyzdžiui, metilas, etilas, propilas (n- ir izo-propilas), butilas (n-, sek-, ižo- ir tret-butilas) , 1, 1-dimetilpropilas ir 1,1-dimetilbutilas. Alkenilo ir alkinilo grupės taip pat gali būti linijinės arba šakotos. Tai 1,1-dimetilbut-3-enilas ir 1,l-dimetilprop-2-inilas.The residues of the alkyl group and other alkyl-containing groups may be linear or branched. These include, for example, methyl, ethyl, propyl (n- and iso-propyl), butyl (n-, sec-, iso- and tert-butyl), 1,1-dimethylpropyl and 1,1-dimethylbutyl. Alkenyl and alkynyl groups may also be linear or branched. They are 1,1-dimethylbut-3-enyl and 1,1-dimethylprop-2-ynyl.

Halogenas apima fluorą, chlorą ir bromą.Halogen includes fluorine, chlorine and bromine.

Pasirenkami fenilo pakaitai apima halogeną, Cx_4 alkilą (pavyzdžiui, metilą) , Cx_4 alkoksilą (pavyzdžiui, metoksilą) , Cx_4 alkiltio- (pavyzdžiui, metiltio) , trifluormetilą, trif luormetoksi, nitro, ciano, Cx_4 alkoksikarbonilą, amino ir mono- ir di (Cx_4) alkilaminą.Optional substituents include halogen, phenyl, C x _ 4 alkyl (such as methyl), C x _ 4 alkoxy (for example methoxy), C x _ 4 alkylthio (for example methylthio), trifluoromethyl, Trif luormetoksi, nitro, cyano, C x _ 4 alkoxycarbonyl, amino and mono- and di (C x _ 4) alkylamino.

Pagal vieną šio išradimo aspektų siūlomi (I) formulės junginiai, kur A ir B nepriklausomai yra H, fluoras, chloras, bromas su sąlyga, jei A ir B abu nėra H; D ir E abu yra H, R yra vandenilis arba Cx_4 alkilas; R yra Cx_4 alkilas, Cx_4 alkoksi arba fenilas, arba R1 ir R2 kartu su azoto atomu, prie kurio jie prijungti, sudaro morfolino, piperidino, pirolidino arba azetidino žiedą; R3 yra vandenilis; R4 yra C3_6 alkilas (galimai pakeistas halogenu, metoksi-, metiltio arba metilsulfonilu), ciklopropilas (galimai pakeistas metilu) , C3_6 alkenilas, C3_6 alkinilas, Cx_4 alkoksi arba CH3ON=C (CN) grupė; o X ir Y yra deguonis.According to one aspect of the present invention there is provided compounds of formula (I) wherein A and B are independently H, fluorine, chlorine, bromine, provided A and B are not both H; D and E are both H, and R is hydrogen or C x _ 4 alkyl; R is C x _ 4 alkyl, C x _ 4 alkoxy, or phenyl, or R 1 and R 2 together with the nitrogen atom to which they are attached form a morpholine, piperidine, pyrrolidine or azetidine ring; R 3 is hydrogen; R 4 is C 3 _ 6 alkyl (optionally substituted with halogen, methoxy, methylthio or methylsulphonyl), cyclopropyl (optionally substituted by methyl), C 3 _ 6 alkenyl, C 3 _ 6 alkynyl, C x _ 4 alkoxy or CH 3 ON = C (CN) group; and X and Y are oxygen.

Pagal kitą išradimo aspektą siūlomi (I) formulės junginiai, kurioje A yra chloras; B, D ir E yra vandenilis; R1 yra vandenilis, metilas arba etilas; R2 yra metilas, etilas arba fenilas, arba R1 ir R2 kartu su azoto atomu, prie kurio jie prijungti, sudaro morfolino arba piperidino žiedą; R3 yra vandenilis; R4 yra C3.4 alkilas (pavyzdžiui, izopropilas arba tret-butilas) arba ciklopropilas; o X ir Y yra deguonis.According to another aspect of the invention there are provided compounds of formula (I) wherein A is chloro; B, D and E are hydrogen; R 1 is hydrogen, methyl or ethyl; R 2 is methyl, ethyl or phenyl, or R 1 and R 2 together with the nitrogen atom to which they are attached form a morpholine or piperidine ring; R 3 is hydrogen; R 4 is C 3 . 4 alkyl (e.g., isopropyl or tert-butyl) or cyclopropyl; and X and Y are oxygen.

Dar kitu aspektu šiame išradime siūlomi (I) formulės junginiai, kurioje A yra chloras; B, D ir E yra 1 2 vandenilis; R ir R nepriklausomai yra metilas arba etilas (geriau abu etilai ir abu metilai) arba kartu su azoto atomu, prie kurio jie prijungti, sudaro morfolino arba piperidino žiedą; R3 yra vandenilis; R4 yra izopropilas, tret-butilas arba ciklopropilas; o X ir Y yra deguonis.In yet another aspect, the present invention provides compounds of formula (I) wherein A is chloro; B, D and E are hydrogen; R and R are independently methyl or ethyl (preferably both ethyl and both methyl) or together with the nitrogen atom to which they are attached form a morpholine or piperidine ring; R 3 is hydrogen; R 4 is isopropyl, tert-butyl or cyclopropyl; and X and Y are oxygen.

Pagal dar vieną išradimo aspektų siūlomas junginys, kurio formulė (1.1) :According to another aspect of the invention there is provided a compound having the formula (1.1):

kurioje A ir B yra nepriklausomai chloras, bromas arba metilas, arba B yra H; Z yra fluoras, chloras, bromas, metilas, etilas arba metoksi grupė. Iš šių junginių reikia pažymėti tuos, kuriuose B yra H ir tuos, kur A ir B abu yra chloras arba metilas. Ypatingai Įdomūs yra junginiai, kur A yra chloras; B yra H, o Z yra toks, kaip pažymėta aukščiau; ir tie, kur A yra chloras arba bromas; B yra H, arba abu A ir B yra chloras; Z yra metilas.wherein A and B are independently chloro, bromo or methyl, or B is H; Z is fluorine, chlorine, bromine, methyl, ethyl or methoxy. Of these compounds, those in which B is H and those in which A and B are both chlorine or methyl are to be noted. Of particular interest are compounds wherein A is chloro; B is H and Z is as noted above; and those wherein A is chlorine or bromine; B is H, or both A and B are chloro; Z is methyl.

II ir III lentelėse.In Tables II and III.

Šis išradimas iliustruojamas pavyzdžiais, pateiktais I,The present invention is illustrated by the following Examples,

Jungi- nio Nr. Jungian nio No. R1 R 1 r2 r 2 r3 r 3 R4 R 4 Lyd.t. (°C) Melting point (° C) 1 1 ch3 ch 3 ch3 ch 3 H H (CH3) 2ch(CH 3 ) 2 ch 182-184 182-184 2 2 c2h5 c 2 h 5 c2h5 c 2 h 5 H H (CH3) 2ch(CH 3 ) 2 ch 154-157 154-157 3 3 -(CH2)2O-(CH2)2-- (CH 2 ) 2 O - (CH 2 ) 2 - H H (CH3)2CH(CH 3 ) 2 CH 180-182 180-182 4 4 -(C - (C h2)s-h 2 ) s- H H (CH3) 2ch(CH 3 ) 2 ch 182-184 182-184 5 5 ch3 ch 3 ch3 ch 3 H H (CH3)3C(CH 3 ) 3 C 202-203 202-203 6 6th ch3 ch 3 ch3 ch 3 H H k- k- 179-180 179-180 7 7th c2h5 c 2 h 5 H H H H (CH3)2CH(CH 3 ) 2 CH 189-190 189-190 8 8th H H C6H5 C 6 H 5 H H (CH3)2CH(CH 3 ) 2 CH 223-224 223-224 9 9th ch3 ch 3 ch3 ch 3 H H C13CC1 3 C 185-186 185-186 10 10th ch3 ch 3 ch3 ch 3 H H C1CH2 (CH3) 2cC1CH 2 (CH 3 ) 2 c 179-181 179-181 11* 11 * ch3 ch 3 ch3 ch 3 - - ch2-c (CH3) 2-ch 2 -c (CH 3 ) 2 - 122-123 122-123 12 12th ch3 ch 3 ch3 ch 3 H H CH3S (CH3)CHCH 3 S (CH 3 ) CH 158-161 158-161 13 13th ch3 ch 3 ch3 ch 3 H H 155-156 155-156 14 14th ch3 ch 3 ch3 ch 3 H H CH3CH2 (CH3) 2cCH 3 CH 2 (CH 3 ) 2 c 155-156 155-156 15 15th ch3 ch 3 ch3 ch 3 H H ch3ch2ch2 (CH3) 2cch 3 ch 2 ch 2 (CH 3 ) 2 c 125-126 125-126 16 16th ch3 ch 3 ch3 ch 3 H H Br (CH3) 2CBr (CH 3 ) 2 C 181.5-182 181.5-182

Junginys Nr. 11 turi formulę:Compound no. 11 has the formula:

χ LENTELĖ (Tęsinys)TABLE ((Continued)

Jungi- nio Nr. Jungian nio No. R1 R 1 R2 R 2 R3 R 3 R4 R 4 Lyd.t. <°C) Melting point <° C) 17 17th ch3 ch 3 ch3 ch 3 H H Cl (CH3) 2CCl (CH 3 ) 2 C 168-169 168-169 18 18th ch3 ch 3 ch3 ch 3 H H CH2=CHCH2 (CH3) 2CCH 2 = CHCH 2 (CH 3 ) 2 C 120-121.5 120-121.5 19 19th ch3 ch 3 ch3 ch 3 H H (C1)2CH(CH3)2C(C 1) 2 CH (CH 3 ) 2 C 180-181 180-181 20 20th ch3 ch 3 ch3 ch 3 H H (CH3)3CO(CH 3 ) 3 CO 206-207 206-207 21 21st ch3 ch 3 ch3 ch 3 H H CH3O (CH3) 2CCH 3 O (CH 3 ) 2 C 141-143 141-143 22 22nd ch3 ch 3 ch3 ch 3 H H CH3S (CH3) 2cCH 3 S (CH 3 ) 2 c 133.5-135 133.5-135 23 23rd ch3 ch 3 ch3 ch 3 H H ch3so2(CH3) 2cch 3 so 2 (CH 3 ) 2 c 169-170 169-170 24 24th ch3 ch 3 ch3 ch 3 H H (CH3)2N(CH 3 ) 2 N 125-126 125-126 25 25th ch3 ch 3 ch3 ch 3 H H (CH3) 3cch2 (CH 3 ) 3 cch 2 194-195.5 194-195.5 26 26th ch3 ch 3 ch3 ch 3 H H HC C (CH3) 2CHC C (CH 3 ) 2 C 179-181 179-181 27 27th ch3 ch 3 ch3 ch 3 H H BrCH2(Br)2CBrCH 2 (Br) 2 C 192.5-193.3 192.5-193.3 28 28th ch3 ch 3 ch3 ch 3 H H BrCHJBr) (CH3)CBrCH (Br) (CH 3 ) C 190 190 29 29th ch3 ch 3 ch3ch2 ch 3 ch 2 H H (CH3)3C(CH 3 ) 3 C 151-153 151-153 30 30th ch3ch2 ch 3 ch 2 ch3ch2 ch 3 ch 2 H H (CH3)3C(CH 3 ) 3 C 161-163 161-163 31 31st ch3 ch 3 (CH3)2CH(CH 3 ) 2 CH H H (CH3)3C(CH 3 ) 3 C 139-141 139-141 32 32 -(CH2)4-- (CH 2 ) 4 - H H (CH3)3c(CH 3 ) 3 c 173-174 173-174 33 33 -( - ( CH2)3-CH 2 ) 3 - H H (CH3)3c(CH 3 ) 3 c 185-187 185-187 34 34 ch3 ch 3 ch3ch2ch2 ch 3 ch 2 ch 2 H H (CH3)3C(CH 3 ) 3 C 175-176 175-176

I lENIEUŠ (Tęsinys)I LENIEUŠ (Continued)

Jungi- nio Nr. Jungian nio No. R1 R 1 b2 b 2 r3 r 3 R4 R 4 Lyd.t. (°C) Melting point (° C) 35 35 ch3 ch 3 ch3och 3 o H H (CH3)3C(CH 3 ) 3 C Oil Oil 36 36 ch3 ch 3 ch3 ch 3 H H (C1)2(CH3)C ch3on=c(C 1) 2 (CH 3 ) C ch 3 is = c 154.5-156.5 154.5-156.5 37 37 ch3 ch 3 ch3 ch 3 H H 1 CN 1 CN 128-129 128-129 38 38 ch3 ch 3 ch3 ch 3 H H F(CH3)2CF (CH 3 ) 2 C 125-128 125-128 39 39 ch3 ch 3 ch3 ch 3 H H CH2=CH(CH3)2CCH 2 = CH (CH 3 ) 2 C 137-139 137-139 40 40 ch3 ch 3 ch3 ch 3 H H ch3och2 (CH3) 2cch 3 och 2 (CH 3 ) 2 c 101-103 101-103 41 41 ch3 ch 3 ch3 ch 3 H H ch3sch2 (CH3)2Cch 3 sch 2 (CH 3 ) 2 C 42 42 ch3 ch 3 ch3 ch 3 H H fch2 (CH3)2Cfch 2 (CH 3 ) 2 C 152-154 152-154 43 43 ch3 ch 3 ch3 ch 3 H H f2ch=ch (CH3) 2cf 2 ch = ch (CH 3 ) 2 c 44 44 ch3 ch 3 ch3 ch 3 H H CH3CH=CH(CH3)2CCH 3 CH = CH (CH 3 ) 2 C 45 45 ch3 ch 3 ch3ch2 ch 3 ch 2 H H Cl (CH3)2CCl (CH 3 ) 2 C 108-111 108-111 46 46th ch3 ch 3 ch3ch2 ch 3 ch 2 H H Br (CH3) 2cBr (CH 3 ) 2 c 133-135 133-135 47 47 ch3 ch 3 ch3ch2 ch 3 ch 2 H H F(CH3)2CF (CH 3 ) 2 C oil oil 48 48 ch3 ch 3 ch3ch2 ch 3 ch 2 H H CH3O (CH3) 2cCH 3 O (CH 3 ) 2 c 136-138 136-138 49 49 ch3 ch 3 ch3ch2 ch 3 ch 2 H H cich2 (ch3)2ccich 2 (ch 3 ) 2 c 50 50 ch3 ch 3 ch3ch2 ch 3 ch 2 H H (CH3) 2ch(CH 3 ) 2 ch 51 51 ch3 ch 3 ch3ch2 ch 3 ch 2 H H CH3 CH 3 52 52 ch3 ch 3 ch3ch2 ch 3 ch 2 H H ch3ch2 (CH3) 2cch 3 ch 2 (CH 3 ) 2 c 130-132 130-132 53 53 ch3 ch 3 ch3ch2 ch 3 ch 2 -ch2--ch 2 - -C(CH3)2--C (CH 3 ) 2 - 54 54 ch3 ch 3 ch3ch2 ch 3 ch 2 H H (CH3)2N(CH 3 ) 2 N 55 55 ch3 ch 3 ch3ch2 ch 3 ch 2 H H ch2=chch2 (ch3) 2cch 2 = chch 2 (ch 3 ) 2 c

I ΙΣΝΙΉΙ£ (Tęsinys)I ΙΣΝΙΉΙ £ (Continued)

Jungi- nio Nr. Jungian nio No. R1 R 1 R2 R 2 7 E' 7th E ' R4 R 4 Lyd.t. (°C) Melting point (° C) 56 56 ch3 ch 3 ch3ch2 ch 3 ch 2 H H (CH3)3CO(CH 3 ) 3 CO 57 57 ch3 ch 3 (CH3) 2ch(CH 3 ) 2 ch H H Cl (CH3) 2cCl (CH 3 ) 2 c 58 58 ch3 ch 3 (CH3)2CH(CH 3 ) 2 CH H H Br (CH3) 2CBr (CH 3 ) 2 C 59 59 ch3 ch 3 (CH3) 2ch(CH 3 ) 2 ch H H F(CH3)2CF (CH 3 ) 2 C 60 60 ch3 ch 3 (CH3) 2ch(CH 3 ) 2 ch H H CH3O (CH3) 2CCH 3 O (CH 3 ) 2 C 61 61 ch3 ch 3 (CH3)2CH(CH 3 ) 2 CH H H C1CH2 (CH3) 2cC1CH 2 (CH 3 ) 2 c 62 62 ch3 ch 3 (CH3)2CH(CH 3 ) 2 CH H H (CH3) 2ch(CH 3 ) 2 ch 63 63 ch3 ch 3 (CH3)2CH(CH 3 ) 2 CH H H 64 64 ch3 ch 3 (CH3) 2ch(CH 3 ) 2 ch H H ch3ch2 (CH3) 2cch 3 ch 2 (CH 3 ) 2 c 65 65 ch3 ch 3 ch3ch2 ch 3 ch 2 H H ch2=ch (CH3) 2cch 2 = ch (CH 3 ) 2 c 111-113 111-113 66 66 ch3 ch 3 ch3 ch 3 H H HC CCH2 (CH3) 2CHC CCH 2 (CH 3 ) 2 C 154-155 154-155 67 67 ch3 ch 3 ch3 ch 3 H H ch3ch=chch2 (CH3)2Cch 3 ch = chch 2 (CH 3 ) 2 C 120 (dec.) 120 (Dec) 68 68 ch3 ch 3 ch3 ch 3 H H CH2=CHCH2CH2(CH3)2CCH 2 = CHCH 2 CH 2 (CH 3 ) 2 C 95-96 95-96

II LENTELĖTABLE II

Junginio Nr. Compound No. R1 R 1 R2 R 2 R3 R 3 R4 R 4 A A B B D D E E Lyd.t. (°C) Melting point (° C) 1 1 ch3 ch 3 ch3 ch 3 H H (CH3)3C(CH 3 ) 3 C CHjD CH3D H H H H H H 143-144 143-144 2 2 ch3 ch 3 ch3 ch 3 H H (CH3)3C(CH 3 ) 3 C CH3 CH 3 H H H H H H 183-185 183-185 3 3 ch3 ch 3 ch3 ch 3 H H (CH3)3C(CH 3 ) 3 C Br Br H H H H H H 219-222 219-222 4 4 ch3 ch 3 ch3 ch 3 H H (CH3)3C(CH 3 ) 3 C F F H H H H H H 125-130 125-130 5 5 ch3 ch 3 ch3 ch 3 H H (ch3)3c(ch 3 ) 3 c Cl Cl Cl Cl H H H H 187-188 187-188 6 6th ch3 ch 3 ch3 ch 3 H H (CH3)3c(CH 3 ) 3 c F F F F F F F F 187-189 187-189 7 7th ch3 ch 3 ch3 ch 3 H H (CH3)3C(CH 3 ) 3 C cf3 cf 3 H H H H H H 198.7-199.6 198.7-199.6 8 8th ch3 ch 3 ch3 ch 3 H H CH3CH2(CH3)2CCH 3 CH 2 (CH 3 ) 2 C F F H H H H H H 110-113 110-113 9 9th ch3 ch 3 CH3CH2 CH3CH 2 H H CH3CH2(CH3)2CCH 3 CH 2 (CH 3 ) 2 C F F H H H H H H Derva Resin 10 10th ch3 ch 3 ch3 ch 3 H H (CH3)3C(CH 3 ) 3 C ch3 ch 3 ch3 ch 3 H H H H 11 11th ch3 ch 3 ch3 ch 3 H H (CH3)3c(CH 3 ) 3 c F F F F H H H H 12 12th ch3 ch 3 ch3 ch 3 H H (CH3)3C(CH 3 ) 3 C Cl Cl F F H H H H 13 13th ch3 ch 3 ch3 ch 3 H H (CH3)3c(CH 3 ) 3 c ch3 ch 3 F F H H H H 14 14th ch3 ch 3 ch3 ch 3 H H (CH3) 3c(CH 3 ) 3 c ch3 ch 3 Cl Cl H H H H 15 15th ch3 ch 3 ch3 ch 3 H H (CH3)3C(CH 3 ) 3 C Br Br F F H H H H 16 16th ch3 ch 3 ch3 ch 3 H H (CH3)3C(CH 3 ) 3 C Cl Cl Br Br H H H H 17 17th ch3 ch 3 ch3 ch 3 H H (CH3)3C(CH 3 ) 3 C Cl Cl H H F F H H 18 18th ch3 ch 3 ch3 ch 3 H H (CH3)3C(CH 3 ) 3 C Cl Cl H H H H F F

II LENTELĖ (tęsinys)TABLE II (cont'd)

Junginio Nr. Compound No. R1 R 1 R2 R 2 R3 R 3 R4 R 4 A A B B D D E E Lyd.t. (CC)Melting point ( C C) 19 19th ch3 ch 3 ch3 ch 3 H H (CH3)3C(CH 3 ) 3 C Br Br H H F F H H 20 20th ch3 ch 3 ch3 ch 3 H H (CH3)3c(CH 3 ) 3 c CF3 CF 3 F F H H H H 21 21st ch3 ch 3 ch3 ch 3 H H Cl (CH3)2CCl (CH 3 ) 2 C Cl Cl Cl Cl H H H H 22 22nd ch3 ch 3 ch3 ch 3 H H Br (CH3) 2CBr (CH 3 ) 2 C Cl Cl Cl Cl H H H H 23 23rd ch3 ch 3 ch3 ch 3 H H F(CH3)2CF (CH 3 ) 2 C Cl Cl Cl Cl H H H H 24 24th ch3 ch 3 ch3 ch 3 H H ch3o (CH3) 2cch 3 o (CH 3 ) 2 c Cl Cl Cl Cl H H H H 25 25th ch3 ch 3 ch3 ch 3 H H CH3CH2(CH3)2CCH 3 CH 2 (CH 3 ) 2 C Cl Cl Cl Cl H H H H 26 26th ch3 ch 3 ch3 ch 3 H H fch2 (CH3) 2cfch 2 (CH 3 ) 2 c Cl Cl Cl Cl H H H H 27 27th ch3 ch 3 ch3 ch 3 H H Cl (CH3) 2cCl (CH 3 ) 2 c Br Br H H H H H H 188-189 188-189 28 28th ch3 ch 3 ch3 ch 3 H H Br (CH3) 2CBr (CH 3 ) 2 C Br Br H H H H H H 184.5-187 184.5-187 29 29th ch3 ch 3 ch3 ch 3 H H F(CH3)2CF (CH 3 ) 2 C Br Br H H H H H H 160-163 160-163 30 30th ch3 ch 3 ch3 ch 3 H H ch3o (CH3) 2cch 3 o (CH 3 ) 2 c Br Br H H H H H H 158-160 158-160 31 31st ch3 ch 3 ch3 ch 3 H H CH3CH2(CH3)2CCH 3 CH 2 (CH 3 ) 2 C Br Br H H H H H H 159-161 159-161 32 32 ch3 ch 3 ch3 ch 3 H H cich2 (CH3) 2ccich 2 (CH 3 ) 2 c Br Br H H H H H H 186-188 186-188 33 33 ch3 ch 3 ch3 ch 3 H H fch2 (CH3) 2cfch 2 (CH 3 ) 2 c Br Br H H H H H H 34 34 ch3 ch 3 ch3 ch 3 H H Cl (CH3) 2cCl (CH 3 ) 2 c ch3 ch 3 H H H H H H 35 35 ch3 ch 3 ch3 ch 3 H H Br (CH3) 2CBr (CH 3 ) 2 C ch3 ch 3 H H H H H H 36 36 ch3 ch 3 ch3 ch 3 H H F(CH3)2CF (CH 3 ) 2 C ch3 ch 3 H H H H H H 37 37 ch3 ch 3 ch3 ch 3 H H ch3o (CH3) 2cch 3 o (CH 3 ) 2 c ch3 ch 3 H H H H H H 38 38 ch3 ch 3 ch3 ch 3 H H CH3CH2(CH3)2CCH 3 CH 2 (CH 3 ) 2 C ch3 ch 3 H H H H H H 39 39 ch3 ch 3 ch3 ch 3 H H fch2 (CH3) 2cfch 2 (CH 3 ) 2 c ch3 ch 3 H H H H H H 40 40 ch3 ch 3 ch3 ch 3 H H ch2=ch (CH3)2Cch 2 = ch (CH 3 ) 2 C Br Br H H H H H H 41 41 ch3 ch 3 ch3 ch 3 H H CH2=CH(CH3)2CCH 2 = CH (CH 3 ) 2 C ch3 ch 3 H H H H H H 42 42 ch3 ch 3 ch3 ch 3 H H CH2=CH(CH3)2CCH 2 = CH (CH 3 ) 2 C Cl Cl Cl Cl H H H H

II LENTELĖ (tęsinys)TABLE II (cont'd)

Junginio Nr. Compound No. R1 R 1 R2 R 2 R3 R 3 R4 R 4 A A B B D D E E Lyd.t. (°C) Melting point (° C) 43 43 ch3 ch 3 ch3ch2 ch 3 ch 2 H H (CH3) 2ch(CH 3 ) 2 ch Cl Cl Cl Cl H H H H 149-150 149-150 44 44 ch3 ch 3 ch3ch2 ch 3 ch 2 H H (CH3)3C(CH 3 ) 3 C Cl Cl Cl Cl H H H H 139-142 139-142 45 45 ch3 ch 3 ch3ch2 ch 3 ch 2 H H (CH3)3c(CH 3 ) 3 c ch3 ch 3 H H H H H H 46 46th ch3 ch 3 ch3ch2 ch 3 ch 2 H H (CH3)3C(CH 3 ) 3 C Br Br H H H H H H 148-150 148-150 47 47 ch3 ch 3 ch3ch2 ch 3 ch 2 H H (CH3)3C(CH 3 ) 3 C F F F F H H H H 48 48 ch3 ch 3 ch3ch2 ch 3 ch 2 H H (CH3)3c(CH 3 ) 3 c CH3 CH 3 CH3 CH 3 H H H H 49 49 ch3 ch 3 ch3ch2 ch 3 ch 2 H H F(CH3)2CF (CH 3 ) 2 C Br Br H H H H H H 97-100 97-100 50 50 ch3 ch 3 ch3ch2 ch 3 ch 2 H H F(CH3)2CF (CH 3 ) 2 C ch3 ch 3 H H H H H H 51 51 ch3 ch 3 ch3ch2 ch 3 ch 2 H H F(CH3)2CF (CH 3 ) 2 C Cl Cl Cl Cl H H H H 52 52 ch3 ch 3 ch3ch2 ch 3 ch 2 H H F(CH3)2CF (CH 3 ) 2 C F F F F H H H H 53 53 ch3 ch 3 ch3ch2 ch 3 ch 2 H H (CH3) 2ch(CH 3 ) 2 ch Br Br H H H H H H 54 54 ch3 ch 3 ch3ch2 ch 3 ch 2 H H (CH3) 2ch(CH 3 ) 2 ch ch3 ch 3 H H H H H H 55 55 ch3 ch 3 ch3ch2 ch 3 ch 2 H H (CH3) 2ch(CH 3 ) 2 ch F F F F H H H H 56 56 ch3 ch 3 ch3ch2 ch 3 ch 2 H H fch2 (CH3) 2cfch 2 (CH 3 ) 2 c Br Br H H H H H H 57 57 ch3 ch 3 ch3ch2 ch 3 ch 2 H H CH3CH2(CH3)2CCH 3 CH 2 (CH 3 ) 2 C Br Br H H H H H H 144-147 144-147 58 58 ch3 ch 3 CH(CH3)2 CH (CH 3 ) 2 H H (CH3)3c(CH 3 ) 3 c Br Br H H H H H H 59 59 ch3 ch 3 CH(CH3)2 CH (CH 3 ) 2 H H (CH3)3C(CH 3 ) 3 C ch3 ch 3 H H H H H H 60 60 ch3 ch 3 CH(CH3)2 CH (CH 3 ) 2 H H F(CH3)2CF (CH 3 ) 2 C Br Br H H H H H H 61 61 ch3 ch 3 CH(CH3)2 CH (CH 3 ) 2 H H fch2 (CH3) 2cfch 2 (CH 3 ) 2 c Cl Cl Cl Cl H H H H 62 62 ch3 ch 3 CH(CH3)2 CH (CH 3 ) 2 H H F(CH3)2CF (CH 3 ) 2 C ch3 ch 3 H H H H H H 63 63 ch3 ch 3 ch3ch2 ch 3 ch 2 H H Br (CH3) 2CBr (CH 3 ) 2 C Br Br H H H H H H 108-110 108-110 64 64 ch3 ch 3 ch3ch2 ch 3 ch 2 H H Cl (CH3) 2CCl (CH 3 ) 2 C Br Br H H H H H H 119-121 119-121 65 65 ch3 ch 3 ch3ch2 ch 3 ch 2 H H C1CH2(CH3)2CC1CH 2 (CH 3) 2 C Br Br H H H H H H 154-155 154-155 66 66 ch3 ch 3 ch3ch2 ch 3 ch 2 H H ch3o (CH3) 2cch 3 o (CH 3 ) 2 c Br Br H H H H H H 133-134 133-134

II LENTELĖ (tęsinys)TABLE II (cont'd)

Junginio Nr. Compound No. R1 R 1 R2 R 2 R3 R 3 R4 R 4 A A B B D D E E Lyd.t. (°C) Melting point (° C) 67 67 ch3 ch 3 CH(CH3)2 CH (CH 3 ) 2 H H CH3O (CH3) 2cCH 3 O (CH 3 ) 2 c Br Br H H H H H H Gum Gum 68 68 ch3 ch 3 ch3 ch 3 1/ CH3 1 / CH 3 Br Br H H H H H H 185-188 185-188 69* 69 * ch3 ch 3 ch3ch2 ch 3 ch 2 -CH2-C (CH3) 2--CH 2 -C (CH 3 ) 2 - Br Br H H H H H H Gum Gum

Junginys Nr. 69 turi formulę:Compound no. 69 has the formula:

OO

IIII

III LENTELĖTABLE III

E AE A

D BD B

Jun- ginys Jun- ginys R1 R 1 R2 R 2 R4 R 4 A A B B D D E E X X Y Y Lyd.t. (°C) Melting point (° C) 1 1 ch3 ch 3 ch3 ch 3 (CH3)3C(CH 3 ) 3 C Cl Cl H H H H H H 0 0 S S 164-167 164-167 2 2 ch3 ch 3 ch3 ch 3 (CH3)3C(CH 3 ) 3 C Cl Cl H H H H H H S S 0 0 120 (dec.) 120 (Dec) 3 3 ch3 ch 3 ch3 ch 3 (CH3)3C(CH 3 ) 3 C Cl Cl H H H H H H S S s s 154-156 154-156

Šio išradimo junginius galima gauti, pavyzdžiui, I-II reakcijos schemose parodytais būdais. Visose schemose R1, R2, R4, A, B, D ir E yra tokie, kaip pažymėta aukščiau.The compounds of the present invention may be obtained, for example, by the methods outlined in Reaction Schemes I-II. In all schemes, R 1 , R 2 , R 4 , A, B, D and E are as noted above.

Pagal I schemą (II) formulės junginius galima gauti reaguojant (VI) formulės junginiui su chloranhidridu R COC1 tinkamame organiniame tirpiklyje, tokiame kaip metileno chloridas arba toluenas, esant bazei, tokiai kaip tretinis aminas (pavyzdžiui, trietilaminas) arba šarminio metalo karbonatui arba hidroksidui (pavyzdžiui, natrio bikarbonatui arba hidroksidui).In Scheme I, compounds of formula (II) can be obtained by reacting a compound of formula (VI) with chloro anhydride R COC1 in a suitable organic solvent such as methylene chloride or toluene in the presence of a base such as tertiary amine (e.g. triethylamine) or alkali metal carbonate or hydroxide. such as sodium bicarbonate or hydroxide).

(VI) formulės junginius galima gauti redukuojant (V) formulės junginius žinomais iš literatūros standartiniais metodais, pavyzdžiui, geležies milteliais vandeniniame etanolyje.Compounds of formula (VI) may be obtained by reduction of compounds of formula (V) by methods known in the literature, such as iron powder in aqueous ethanol.

(V) formulės amidus galima gauti iš (III) formulės junginių, iš pradžių paverčiant jungini (III) chloranhidridu (IV) , veikiant standartiniu reagentu, tokiu kaip tionilchloridas arba oksalilchloridas. Po to chloranhidridas (IV) veikiamas aminu RXR2NH tinkamame organiniame tirpiklyje (pavyzdžiui, metilenchloride arba toluene) arba vandenyje, dalyvaujant šarmui (tokiam kaip trietilaminas arba natrio bikarbonatas, arba amino R1R2NH pertekliuje) .The amides of formula (V) can be obtained from the compounds of formula (III) by first converting the compound (III) into the chloro anhydride (IV) using a standard reagent such as thionyl chloride or oxalyl chloride. The chloro anhydride (IV) is then treated with the amine R X R 2 NH in a suitable organic solvent (e.g. methylene chloride or toluene) or water in the presence of an alkali (such as triethylamine or sodium bicarbonate or excess amino R 1 R 2 NH).

Pagal 2 reakcijos schemą (II) formulės junginius galima gauti iš (IX) formulės junginių, reaguojant jiems su aminu R R NH tinkamame organiniame tirpiklyje, tokiame kaip metilenchloridas arba tetrahidrofuranas (THF) dalyvaujant šarmui, kaip trietilaminas, natrio bikarbonatas arba R1R2NH pertekliuje.In Scheme 2, compounds of formula (II) may be prepared from compounds of formula (IX) by reaction with amine RR NH in an appropriate organic solvent such as methylene chloride or tetrahydrofuran (THF) in the presence of an alkali such as triethylamine, sodium bicarbonate or R 1 R 2 NH in excess.

SchemaSchematic

(II)(II)

SchemaSchematic

(II) ( IX)(II) (IX)

SchemaSchematic

BB

R (X) (XI ) (IX) formulės chloranhidridus galima gauti reaguojant karboninėms rūgštims (VIII) su standartiniu reagentu, tokiu kaip oksalilchloridas, tinkamame sausame tirpiklyje, tokiame kaip THF arba metilenchloridas, pridedant, jei reikia, katalitinį DMF kiekį.The chloro anhydrides of formula R (X) (XI) (IX) can be obtained by reacting carbonic acids (VIII) with a standard reagent such as oxalyl chloride in a suitable dry solvent such as THF or methylene chloride, if necessary with the addition of a catalytic amount of DMF.

Karbonines rūgštis (VIII) galima gauti iš atitinkamos pakeistos 4-aminobenzoinės rūgšties (VII), jai reaguojant su chloranhidridu R4COC1 vandenyje, dalyvaujant bent dviems ekvivalentams šarmo, tokio kaip šarminio metalo karbonatas arba hidroksidas (pavyzdžiui, natrio bikarbonatas). Pakeistas 4-amidobenzoines rūgštis (VII) galima gauti žinomais būdais.Carboxylic acids (VIII) can be obtained from the corresponding substituted 4-aminobenzoic acid (VII) by reaction with the chloro anhydride R 4 in COCl 1 in water in the presence of at least two equivalents of an alkali such as an alkali metal carbonate or hydroxide (e.g. sodium bicarbonate). Substituted 4-amidobenzoic acids (VII) can be obtained by known methods.

Pagal 3 reakcijos schemą (XI) formulės junginiai, kurioje R5 ir R6 yra vandenilis, Cx.4 alkilas arba halogenas, gaunami iš junginių (X), kur X' yra chloras, bromas arba jodas, veikiant šarminio metalo hidroksidu (pavyzdžiui, natrio) dvifazinėje sistemoje, susidedančioje iš organinio tirpiklio, kaip metilenchloridas, ir vandens, dalyvaujant heterogeniniam katalizatoriui (pavyzdžiui, tetrabutilamonio bromidui).In Scheme 3, compounds of formula (XI) wherein R 5 and R 6 are hydrogen, C x . 4 alkyl or halogen obtained from compounds (X) wherein X 'is chlorine, bromine or iodine, by treatment with an alkali metal hydroxide (e.g. sodium) in a biphasic system consisting of an organic solvent such as methylene chloride and water in the presence of a heterogeneous catalyst (e.g. , for tetrabutylammonium bromide).

Pagal 4 reakcijos schemą (VIII) formulės tarpinį junginį galima gauti, hidrolizuoj ant junginį (XIV) standartiniais metodais, pavyzdžiui, veikiant vandenine neorganine rūgštimi (pavyzdžiui, vandenine sieros rūgštimi) arba vandeniniu šarmu (pavyzdžiui, vandeniniu hidroksidu, esant arba nesant antram tirpikliui, tokiam kaip etanolis) arba diazotinant vandeninėje aplinkoje (pavyzdžiui, natrio nitritu vandeninėje sieros rūgštyje). (XIV) formulės junginius galima gauti hidrolizuojant (XIII) junginius standartiniais metodais, pavyzdžiui, veikiant vandenine neorganine rūgštimi (pavyzdžiui, vandenine sieros rūgštimi) arba vandeniniu šarmu (pavyzdžiui, vandeniniu natrio hidroksidu su antru tirpikliu, kaip etanolis arba be jo) arba vandeniniu šarminiu peroksidu (pavyzdžiui, vandeniniu vandenilio peroksidu) , kuriame yra natrio hidroksido su antru tirpikliu, kaip etanolis arba be jo. (XIII) formulės junginius galima gauti iš (XII) junginių, jiems reaguojant su chloranhidridu R4COC1 tinkamame organiniame tirpiklyje (pavyzdžiui, metilenchloride arba toluole), dalyvaujant šarmui, kaip tretiniams aminams (pavyzdžiui, trietilaminas) arba šarminio metalo karbonatui arba hidroksidui (pavyzdžiui, natrio karbonatui arba hidroksidui).In Scheme 4, an intermediate of formula (VIII) can be obtained by hydrolysis of compound (XIV) by standard methods, for example, by treatment with an aqueous inorganic acid (e.g., aqueous sulfuric acid) or an aqueous alkali (e.g., aqueous hydroxide). such as ethanol) or diazotizing in an aqueous medium (e.g., sodium nitrite in aqueous sulfuric acid). Compounds of formula (XIV) may be obtained by hydrolysis of compounds of formula (XIII) by standard methods, for example, by treatment with an aqueous inorganic acid (e.g., aqueous sulfuric acid) or aqueous alkali (e.g., aqueous sodium hydroxide with or without a second solvent, ethanol) peroxide (e.g., aqueous hydrogen peroxide), containing sodium hydroxide with or without a second solvent, such as ethanol. Compounds of formula (XIII) may be prepared from compounds of formula (XII) by reaction with chloro-anhydride R 4 COCl in a suitable organic solvent (e.g., methylene chloride or toluene) in the presence of alkali as tertiary amines (e.g. triethylamine) or alkali metal carbonate or hydroxide , such as sodium carbonate or hydroxide).

(XIII)(XIII)

(VIII) (XIV)(VIII) (XIV)

Pagal 5 reakcijos schemą (VIII) formulės junginius galima gauti hidrolizuojant esteri (XVI), kur R7 yra Cf.4 alkilas, šarminio metalo hidroksidų (pavyzdžiui, natrio hidroksidų) tinkamame tirpiklyje, tokiame kaip vanduo arba etanolis, arba jų mišinyje. (XVI) formulės esteri galima gauti iš (XV) formulės aminobenzoinės rūgšties esterio keliais būdais. Iš pradžių vykdoma reakcija su R4COC1 chloranhidridu tinkamame organiniame tirpiklyje (pavyzdžiui, metilenchloride arba toluene), dalyvaujant šarmui, kaip tretinis aminas (pavyzdžiui, trietilaminas) arba šarminio metalo karbonatui arba hidroksidui. Be to, jei bet kuris iš A, B, D ir E pakaitų yra stiprus elektronų akceptorius, tai (XV) aminoeterio protoną galima pašalinti stipriu šarmu (pavydžiui, natrio hidroksidu arba ličio diizopropilamidu) inertiniame organiniame tirpiklyje (pavyzdžiui, tetrahidrofurane arba dimetoksietane), o po to paveikti chloranhidridu R4COC1. Norint gauti patenkinamą išeigą, galima pridėti du ekvivalentus stipraus šarmo.In Scheme 5, compounds of formula (VIII) may be obtained by hydrolysis of an ester (XVI) wherein R 7 is C 1-4 alkyl in an alkali metal hydroxide (e.g., sodium hydroxide) in a suitable solvent such as water or ethanol, or a mixture thereof. The ester of formula (XVI) can be obtained from the aminobenzoic acid ester of formula (XV) in several ways. Initially, the reaction is carried out with R 4 COCl chlorohydride in a suitable organic solvent (e.g. methylene chloride or toluene) in the presence of an alkali such as a tertiary amine (e.g. triethylamine) or an alkali metal carbonate or hydroxide. In addition, if any of the substituents A, B, D and E is a strong electron acceptor, the proton (XV) amino ether can be removed with a strong alkali (e.g. sodium hydroxide or lithium diisopropylamide) in an inert organic solvent (e.g. tetrahydrofuran or dimethoxyethane), and then treated with chloro-anhydride R 4 COC1. Two equivalents of strong alkali can be added to obtain a satisfactory yield.

(XV) formulės junginius galima gauti iš (VII) formulės junginių, reaguojant jiems su alkanoliu R?OH, kur R7 yra Cx„4 alkilas, dalyvaujant rūgštiniam katalizatoriui (pavyzdžiui, koncentruotai sieros rūgščiai arba dujiniam HCl) .Compounds of formula (XV) may be prepared from compounds of formula (VII) by reaction with an alkanol R ? OH where R 7 is C x 4 alkyl in the presence of an acidic catalyst (e.g. concentrated sulfuric acid or gaseous HCl).

SchemaSchematic

D B (VIII)D B (VIII)

D B (XVI)D B (XVI)

Pagal 6 reakcijos schemą (XVIII) formulės junginius, kurioje kiekvienas iš R8 ir R9 nepriklausomai yra H, Cx_4 alkilas arba Cx_4 halogenalkilas, galima gauti veikiant (XVII) fluorido pernešimo reagentu (pavyzdžiui, sidabro tetrafluorboratu) tinkamame tirpiklyje (pavyzdžiui, acetonitrile).According to Reaction Scheme 6. Compounds (XVIII) Compounds of formula I wherein each of R 8 and R 9 are independently H, C x _ 4 alkyl or C x _ 4 haloalkyl, can be obtained compounds of formula (XVII) fluoride transfer reagent (for example silver tetrafluoroborate) in a suitable in a solvent (such as acetonitrile).

SchemaSchematic

11 ‘V 11 'V

F RF R

(XVII)(XVII)

Pagal 7 reakcijos schemą (XX) formulės junginius, kurioje R ir R yra tokie, kaip 6 schemoje, galima gauti veikiant (XIX) formulės hidroksijunginius fluorinančia medžiaga (pavyzdžiui, dietilamino sieros trifluoridu) tinkamame tirpiklyje (pavyzdžiui, metilenchloride). (XX) formulės junginius taip pat galima gauti, reaguojant (VI) formulės junginiams su (XXXV) chloranhidridu tinkamame tirpiklyje (tokiame kaip metilchloridas arba etilo acetatas), dalyvaujant šarmui (kaip trietilaminas arba kalio karbonatas).In Scheme 7, compounds of formula (XX) wherein R and R are as in Scheme 6 can be obtained by reacting a hydroxy compound of formula (XIX) with a fluorinating agent (e.g., diethylamine sulfur trifluoride) in a suitable solvent (e.g., methylene chloride). Compounds of formula (XX) may also be prepared by reacting compounds of formula (VI) with (XXXV) chlorohydride in an appropriate solvent (such as methyl chloride or ethyl acetate) in the presence of an alkali (such as triethylamine or potassium carbonate).

SchemaSchematic

Pagal 8 j unginius (VI) reakcij os galima (XXXV) (XXII) formulių junginį (II) schemą (XXI) ir gauti, veikiant tionuojančia medžiaga (pavyzdžiui, fosforo pentasulfidu arba Lavesono reagentu) tinkamame tirpiklyje (pavyzdžiui, toluole arba acetonitrile). Kiekvieną iš junginių (XXI) ir (XXII) galima gauti mišinyje, po to išskiriant chromatografiškai arba perkristalizuojant, arba galima gauti (XXI) junginį, po to jį paversti (XXII).The 8 compounds of Reaction (VI) can be prepared by reacting a compound of Formula (XXXV) (XXII) with Scheme (XXI) and treatment with a thionating agent (e.g., phosphorus pentasulfide or Laveson's reagent) in a suitable solvent (e.g., toluene or acetonitrile). Each of the compounds (XXI) and (XXII) can be obtained in a mixture followed by chromatography or recrystallization, or the compound (XXI) can be obtained followed by conversion to (XXII).

schema t/scheme t /

A/ a'A / a '

(II)(II)

NN

N t1 ,2 (XXII) schemaSchematic of N t 1 , 2 (XXII)

(XXVII) (XXVIII)(XXVII) (XXVIII)

Pagal 9 schemą (XXIV) formulės junginius galima gauti, reaguojant izotiocianatams (XXIII) su R Li arba R MgHal tipo metaloorganiniais reagentais, kur Hal yra halogenas, chloras arba bromas, tinkamame tirpiklyje (tetrahidrofurane) -78°C - +25°C temperatūroje.According to Scheme 9, compounds of formula (XXIV) can be obtained by reacting isothiocyanates (XXIII) with organometallic reagents of the type R Li or R MgHal wherein Hal is halogen, chlorine or bromine in a suitable solvent (tetrahydrofuran) at -78 ° C to + 25 ° C. .

(XXIII) formulės izotiocianatus galima gauti iš (VI) junginių pagal standartines metodikas, pavyzdžiui, veikiant (VI) junginius tiofosgenu.Isothiocyanates of formula (XXIII) can be obtained from compounds of formula (VI) according to standard procedures, for example by treating compounds of formula (VI) with thiophosgene.

(XXIV) formulės junginius taip pat galima gauti iš (XXV) junginių pagal standartines amidų gavimo metodikas. Pavyzdžiui, (XXV) galima paversti chloranhidridu (XXVI), veikiant chlorinančiais reagentais (pavyzdžiui, oksalilchloridu arba tionilchloridu), o chloranhidridas (XXVI) gali reaguoti su aminu R R NH, dalyvaujant šarmui (pavyzdžiui, trietilaminui arba kalio karbonatui). (XXV) formulės karboninės rūgštis galima gauti, hidrinant (XXVII) formulės esterius standartiniais metodais (pavyzdžiui, natrio hidroksidu metanole). Savo ruožtu, (XXVII) esterius galima gauti, reaguojant (XXVIII) junginiams su tionuojančiu reagentu (pavyzdžiui, fosforo pentasulfidu arba Lavesono reagentu) tinkamame tirpiklyje (pavyzdžiui, toluene arba acetonitrile).Compounds of formula (XXIV) may also be obtained from compounds of formula (XXV) according to standard amide preparation procedures. For example, (XXV) can be converted to chloro anhydride (XXVI) by the action of chlorinating agents (e.g., oxalyl chloride or thionyl chloride) and chloro anhydride (XXVI) can be reacted with an amine R R NH in the presence of an alkali (e.g. triethylamine or potassium carbonate). Carboxylic acids of formula (XXV) can be obtained by hydrogenation of esters of formula (XXVII) by standard methods (for example, sodium hydroxide in methanol). In turn, (XXVII) esters can be obtained by reacting (XXVIII) compounds with a thionating agent (e.g., phosphorus pentasulfide or Laveson's reagent) in a suitable solvent (e.g., toluene or acetonitrile).

Pagal 10 reakcijos schemą (XXXII) formulės junginius, kurioje R11 yra Ο4.4 alkilas, galima gauti, reaguojant junginiams (XIX) su Ru-Hal, kur Hal yra chloras, bromas arba jodas, dalyvaujant šarmui, tokiam kaip šarminio metalo karbonatas, oksidas arba hidroksidas (pavyzdžiui, bario oksidas) tinkamame tirpiklyje (pavyzdžiui, metanole). (XIX) formulės junginius galima gauti, hidrolizuoj ant junginius (XXXI) su šarminio metalo hidroksidu (pavyzdžiui, natrio hidroksidu) tinkamame tirpiklyje (pavyzdžiui, vand.metanole). (XXXI) formulės junginius galima gauti, reaguojant junginiui (VI) su chloranhidridu (XXX) tinkamame tirpiklyje (pavyzdžiui, metilenchloride), dalyvaujant šarmui (pavyzdžiui, triėtilaminui). (XXX) formulės chloranhidridus galima gauti, veikiant (XXIX) formulės hidroksirūgštis anhidridu (R10CO)2O, o po to reagentu, sudarančiu chloranhidridą (pavyzdžiui, tionilchloridu arba oksalilchloridu).Compounds of formula (XXXII) wherein R 11 is Ο 4 according to Reaction Scheme 10. 4 alkyl, obtainable by reaction of compounds (XIX) with R u -Hal where Hal is chlorine, bromine or iodine in the presence of an alkali such as an alkali metal carbonate, oxide or hydroxide (e.g. barium oxide) in a suitable solvent (e.g. methanol) ). Compounds of formula (XIX) may be obtained by hydrolysis of compounds (XXXI) with an alkali metal hydroxide (e.g., sodium hydroxide) in a suitable solvent (e.g., water methanol). Compounds of formula (XXXI) may be prepared by reacting compound (VI) with chloro anhydride (XXX) in a suitable solvent (e.g., methylene chloride) in the presence of an alkali (e.g., triethylamine). The chloro anhydrides of formula (XXX) can be obtained by reacting the hydroxy acids of formula (XXIX) with anhydride (R 10 CO) 2 O, followed by the reagent forming the chloro anhydride (e.g., thionyl chloride or oxalyl chloride).

schemascheme

R® 0R @ 0

I IIII

HOCH--C —C 2 I o \HOCH - C —C 2 I o \

R3 OH (XXIX)R 3 OH (XXIX)

HOCH2-C—cHOCH 2 -C-c

ClCl

(XXXII) t — G // \\ Y r’ n -// \y-c(XXXII) t - G // \\ Y r 'n - // \ y-c

R1XOCH- — C-C ‘ I schemaR 1X OCH- - CC 'I Schematic

Pagal II reakcijos schemą (I) formulės junginius galima gauti iš (XXXIII) junginių, kur L yra atskylanti grupė, pavyzdžiui, fluoras, chloras, bromas, jodas, metansulfoniloksi grupė, trifluormetansulfoniloksi grupė, reaguojant jiems su R4-CO-NH2 formulės junginiu ir šarmu (pavyzdžiui, natrio hidroksidu, ličio diizopropilamidu, šarminių metalų karbonatais arba alkoksidais). (II) formulės junginius galima gauti iš (VI) formulės anilinų pagal 1 schemą. (VI) formulės anilinus galima gauti, reaguojant (XXXIII) junginiams su amoniaku tinkamame tirpiklyje (pavyzdžiui, etanole arba piridine). (VI) formulės junginius galima gauti taip pat iš (XXXIV) formulės junginių, kur M yra azido arba hidrozino grupė, veikiant redukuojančia medžiaga (pavyzdžiui, vandeniliu, dalyvaujant katalizatoriui). Junginius (XXXIV) galima gauti iš (XXXIII) formulės junginių, reaguojant jiems su šarminių metalų azidais (pavyzdžiui, natrio azidu) arba hidrozinu tinkamame tirpiklyje (pavyzdžiui, dimetilformamide arba etanole).In Scheme II, compounds of formula (I) can be obtained from compounds of formula (XXXIII) wherein L is a leaving group such as fluorine, chlorine, bromine, iodine, methanesulfonyloxy, trifluoromethanesulfonyloxy, by reaction with R 4 -CO-NH 2 and alkali (such as sodium hydroxide, lithium diisopropylamide, alkali metal carbonates or alkoxides). Compounds of formula (II) may be obtained from the anilines of formula (VI) according to Scheme 1. The anilines of formula (VI) can be obtained by reacting (XXXIII) compounds with ammonia in a suitable solvent (e.g., ethanol or pyridine). Compounds of formula (VI) may also be obtained from compounds of formula (XXXIV), wherein M is an azido or hydrosine group, under the action of a reducing agent (e.g., hydrogen in the presence of a catalyst). Compounds (XXXIV) can be obtained from compounds of formula (XXXIII) by reaction with alkali metal azides (e.g. sodium azide) or hydrosine in a suitable solvent (e.g. dimethylformamide or ethanol).

Pagal dar vieną iš aspektų išradime pateikiami duoto išradimo junginių gavimo būdai.In another aspect, the invention provides methods of preparing the compounds of the present invention.

Šio išradimo junginiai yra efektyvūs fungicidai ir gali būti taikomi naikinant ar daugiau iš toliau pateiktų patogeninių organizmų:The compounds of the present invention are effective fungicides and can be used to kill one or more of the following pathogenic organisms:

kviečių Puccinia recondita, miežių Erysiphe graminis (miltenį), obuolių Venturia inaequalis (rauplės), žemės riešutų Cercospora arachidicola, vynmedžio Plasmopara viticola Phytophtora infestans. Be to, apdirbant, jie yra efektyvūs prieš viticola ir Phytophtora infestans.wheat Puccinia recondita, barley Erysiphe graminis (powdery mildew), apple Venturia inaequalis (pox), peanut Cercospora arachidicola, Plasmopara viticola Phytophtora infestans. In addition, they are effective against viticola and Phytophtora infestans when treated.

ir bulvių sistemingai Plastmoparaand potatoes systematically Plastmopara

Šiame išradime siūlomas kovos su grybeliais būdas, apdirbant augalus, sėklas arba pažeistas augalų arba sėklų vietas fungicidiniu efektyviu aukščiau nurodyto junginio kiekiu arba kompozicija, turinčia jį savo sudėtyj e.The present invention provides a method of controlling fungi by treating plants, seeds, or damaged areas of plants or seeds with a fungicidal effective amount of a compound of the above or a composition comprising it.

naudojant nešiklius arba šiame išradime siūlomosusing carriers or those of the present invention

Junginius galima naudoti tiesiai agrocheminiais tikslais, bet žymiai patogiau juos įvesti į kompozicijas, dispergentus.The compounds can be used directly for agrochemical purposes, but it is much more convenient to introduce them into compositions, dispersants.

fungicidinės turinčios savo sudėtyje aukščiau nurodytus junginius ir tinkamą nešiklį arba skiediklį.fungicidal compositions containing the above compounds and a suitable carrier or diluent.

Tokiu būdu, kompozicijos,In this way, compositions,

Junginius galima naudoti įvairiais būdais. Pavyzdžiui, juos galima taikyti individualiai arba kaip mišinį, tiesiogiai paveikiant augalų lapus ir aplinką, kurioje auga augalai arba bus sodinami, arba jais galima šlakstyti, purkšti arba patepti kremo arba pastos mišiniu, arba juos galima naudoti kaip garus arba kaip prailginto veikimo granules.The compounds can be used in a variety of ways. For example, they can be applied individually or as a mixture, directly affecting the leaves of the plant and the environment in which the plants will be planted or sprayed, sprayed or applied with a mixture of cream or paste, or used as a vapor or as extended release pellets.

Apdoroti galima bet kurią augalų dalį, įskaitant lapus, stiebus, šakas arba šaknis, arba dirvą apie šaknis, arba sėklas prieš sodinimą, arba apskritai dirvą, tą vandenį, kuriame auga ryžiai, ar hidroponines sistemas. Šio išradimo junginius taip pat galima įvesti augalams injekcijomis arba papurkšti augaliją elektrodinamine purškimo aparatūra arba kitais nesudėtingais būdais.Any part of the plant can be treated, including leaves, stems, branches or roots, or root soil or seed before planting, or soil in general, rice water, or hydroponic systems. The compounds of the present invention may also be administered to plants by injection or sprayed with electrodynamic spraying equipment or other simple means.

Naudojamas terminas augalas apima sėjinukus, krūmus ir medžius. Be to, išradimo fungicidinis būdas taikomas prevencijai, apsaugai, profilaktikai ir išnaikinimui.The term plant used includes seedlings, shrubs and trees. In addition, the fungicidal method of the invention is applicable to prevention, protection, prevention and eradication.

Junginiai agrotechniniams ir žemės ūkio tikslams gerai naudojami kompozicijose. Naudojamos kompozicijos tipas bet kuriuo atveju priklauso nuo konkretaus tikslo.The compounds are well used in compositions for agricultural and agricultural purposes. In any case, the type of composition used depends on the particular purpose.

Kompozicijos gali būti dulkių arba granulių formos, į kurias įeina aktyvus komponentas (šio išradimo junginys) nešiklis, ir kitas skiediklis arba pavyzdžiui, tokie nešikliai, kaip kaolinas, bėntonitas, kizelguras, dolomitas, kalcio karbonatas, talkas, magnio oksido milteliai, žemė, gipsas, diatominė žemė ir molis. Tokios granulės gali būti suformuojamos iš anksto ir įterpiamos į žemę be papildomo apdorojimo. Tas granules galima gauti, impregnuojant užpildo granules aktyviu komponentu arba gaunant aktyvaus komponento ir miltelių užpildo mišinioThe compositions may take the form of dusts or granules comprising the active component (compound of the present invention) carrier and other diluents or, for example, carriers such as kaolin, btontonite, kieselguhr, dolomite, calcium carbonate, talc, magnesium oxide powder, earth, gypsum , diatomaceous earth and clay. Such granules can be preformed and embedded in the ground without further processing. These granules can be obtained by impregnating the filler granules with the active component or by obtaining a mixture of the active component and the powder filler.

Kompozicijoje sėklų apdorojimui gali būti granules.The composition may comprise granules for seed treatment.

medžiaga (pavyzdžiui, mineralinis aliejus), pagerinantis kompozicijos adgeziją sėkloms, be to, apdorojant sėklas, aktyvų komponentą galima įvesti į kompozicijas su organiniu tirpikliu (pavyzdžiui, N-metilpirolidonu, propilenglikoliu arba dimetilformamidu). Kompozicijos taip pat gali būti sukietintų miltelių arba disperguoj amų vandenyje granulių formos, apimančios drėkinančias arba disperguojančias medžiagas, palengvinančias dispergavimąsi skysčiuose. Milteliai ir granulės taip pat gali turėti užpildų ir suspensinių medžiagų.a substance (such as a mineral oil) which improves the adhesion of the composition to the seeds, and in addition to the treatment of the seeds, the active ingredient can be incorporated into compositions with an organic solvent (e.g., N-methylpyrrolidone, propylene glycol or dimethylformamide). The compositions may also be in the form of a solidified powder or water-dispersible granules comprising wetting or dispersing agents which facilitate dispersion in liquids. The powders and granules may also contain fillers and suspensions.

Emulguojančius koncentratus arba emulsijas galima gauti, ištirpinant aktyvų komponentą organiniame tirpiklyje, kuriame gali būti drėkinančios ar emulguojančios medžiagos ir po to sujungiant mišinį su vandeniu, kuriame taip pat gali būti drėkinančios arba emulguojačios medžiagos. Geriausi organiniai tirpikliai yra aromatiniai tirpikliai, tokie kaip alkilbenzolai ir alkilnaftalinai, ketonai, tokie kaip cikloheksanonas ir metilcikloheksanonas, chloruoti angliavandeniliai, tokie kaip chlorbenzolas ir trichloretanas, ir alkoholiai, tokie kaip benzilo alkoholis, furfurilo alkoholis, butanolis ir glikolio eteriai.Emulsifying concentrates or emulsions may be prepared by dissolving the active component in an organic solvent, which may contain wetting or emulsifying agents, and then mixing the mixture with water, which may also contain wetting or emulsifying agents. Preferred organic solvents are aromatic solvents such as alkylbenzenes and alkylnaphthalenes, ketones such as cyclohexanone and methylcyclohexanone, chlorinated hydrocarbons such as chlorobenzene and trichloroethane, and alcohols such as benzyl alcohol, furfuryl alcohol, butanol and glycol ethers.

Praktiškai netirpių kietų dalelių suspensiniai koncentratai gali būti gaunami rutuliniuose malūnuose su disperguojančia medžiaga ir suspenduojančia medžiaga, trukdančia susidaryti nuosėdoms.Practically insoluble solids slurry concentrates can be obtained in ball mills with dispersants and suspending agents to prevent sedimentation.

Kompozicija išpurškimui gali būti aerozolinė, kur mišinys yra konteineryje suspaustas su nešikliu, pavyzdžiui, fluortrichlormetanu arba dichlordifluormetanu.The spray formulation may be aerosolized, wherein the mixture is pressurized in a container with a carrier such as fluorotrichloromethane or dichlorodifluoromethane.

Šio išradimo sausas kompozicijas galima sumaišyti su pirotechniniu mišiniu, gaunant kompoziciją, galinčią uždaroje erdvėje skleisti dūmus, kuriuose yra junginių.The dry compositions of the present invention may be mixed with a pyrotechnic composition to provide a composition capable of emitting fumes containing compounds in a confined space.

Be to, junginiai gali būti mikrokapsulėse. Juos galima Įvesti į biodegraduojančius polimerinius sąstatus, kontroliuojant prailgintą aktyvios medžiagos išsiskycimą.In addition, the compounds may be contained in microcapsules. They can be introduced into biodegradable polymer formulations by controlling the sustained release of the active ingredient.

Įvedant tinkamus priedus, pavyzdžiui, pagerinančius dispergavimą, adheziją ir patvarumą lietui, skirtingas kompozicijas galima geriau pritaikyti skirtingiems tikslams. Gerinant biologini skirtingų mišinių efektyvumą, galima Įvesti kitus priedus. Tokiais priedais gali būti paviršiaus aktyvūs junginiai, gerinantys sudrėkinimą ir laikymąsi mišiniu apdorotuose paviršiuose ir padidinantys aktyvaus komponento judrumą arba papildomai gali turėti priedų aliejaus pagrindu, gerinančių purškimą. Pavyzdžiui, buvo nustatyta, kad kai kurie mineraliniai ir augaliniai aliejai (pavyzdžiui, sojos aliejus ir rapsų aliejus) keletą kartų pagerina efektyvumą, apsaugant lapus, pavyzdžiui nuo Plasmopara viticola.By incorporating suitable additives, for example, to improve dispersion, adhesion and rain resistance, different compositions can be better adapted to different applications. Other additives can be introduced to improve the biological effectiveness of different mixtures. Such additives may include surfactant compounds to improve wetting and adherence to the treated surfaces of the mixture and to enhance the mobility of the active component, or may additionally contain an oil-based additive to enhance spraying. For example, some mineral and vegetable oils (such as soybean oil and rapeseed oil) have been found to improve efficacy several times in protecting leaves such as Plasmopara viticola.

Šio išradimo junginius galima naudoti kaip mišinius su trąšomis (pavyzdžiui, azoto, kalio ar fosforo trąšomis). Geresnės yra kompozicijos, kuriose trąšų granulės yra padengtos junginiais. Tokiose granulėse gali būti iki 25 svorio % junginio. Tokiu būdu šiame išradime siūloma tokia trąšų kompozicija, i kurią Įeina trąša ir (I) formulės junginys arba jo druska arba kompleksinis metalo junginys.The compounds of the present invention can be used as mixtures with fertilizers (e.g. nitrogen, potassium or phosphorus fertilizers). Compositions in which the fertilizer granules are coated with compounds are preferred. Such granules may contain up to 25% by weight of the compound. Thus, the present invention provides a fertilizer composition comprising a fertilizer and a compound of formula (I) or a salt thereof or a complex metal compound.

Drėkstantys milteliai, emulsiniai ir suspensiniai mišiniai paprastai turi paviršiaus aktyvių medžiagų, pavyzdžiui, drėkinančią medžiagą, emulguojančią medžiagą arba suspenduojančią medžiagą. Šios medžiagos gali būti katijoninės, anijoninės arba nejoninės.Moisturizing powders, emulsions and suspensions generally contain surfactants such as wetting agents, emulsifying agents or suspending agents. These materials may be cationic, anionic or nonionic.

Tinkamos katijoninės medžiagos yra ketvirtiniai amonio junginiai, pavyzdžiui, cetiltrimetilamonio bromidas. Tinkamomis anijoninėmis medžiagomis yra muilai, sieros rūgšties alifatinių monoesterių druskos (pavyzdžiui, natrio laurilsulfatas) ir sulfonuotų aromatinių junginių druskos (pavyzdžiui, natrio dodecilbenzolsulfonatas, natrio, kalcio arba amonio ligninsulfonatas, natrio, kalcio arba amonio butilnaftalinsulfonatas ir natrio diizopropil- ir triizopropilnaftalinsulfonatų mišinys).Suitable cationic materials are quaternary ammonium compounds such as cetyltrimethylammonium bromide. Suitable anionics include soaps, salts of aliphatic monoesters of sulfuric acid (e.g. sodium lauryl sulfate) and salts of sulfonated aromatic compounds (e.g.

Tinkamiausios nejonogeninės medžiagos yra etilenoksido kondensacijos produktas su riebiais alkoholiais, tokias kaip oleilo arba cetilo alkoholis arba alkilfenoliais, kaip oktil- arba nonilfenilis ir oktilkrozolis. Kitos nejonogeninės medžiagos - tai daliniai ilgų grandinių riebiųjų rūgščių ir heksitolanhidridų esteriai, nurodytų dalinių esterių ir etilenoksido kondensacijos produktai ir lecitinai.Preferred nonionic materials are ethylene oxide condensation product with fatty alcohols such as oleyl or cetyl alcohol or alkyl phenols such as octyl or nonylphenyl and octylcrozole. Other non-ionic materials include partial esters of long-chain fatty acids and hexitol anhydrides, condensation products of the specified partial esters and ethylene oxide, and lecithins.

Hidrofiliniai koloidai yra tinkamos suspenduojančios medžiagos (pavyzdžiui, poiivinilpirolidonas ir natrio kąrboksimetilceliuliozė) ir brinkstantys moliai, tokie kaip bentonitas arba atapulgitas.Hydrophilic colloids are suitable suspending agents (e.g., polyvinylpyrrolidone and sodium mitoxymethylcellulose) and swelling moles such as bentonite or atapulgite.

Vandeninių dispersijų arba emulsijų kompozicijos paprastai gaminamos koncentruotos aktyvaus komponento koncentracija koncentratas praskiedžiamas vandeniu prieš naudojimą. Tie mišiniai turi būti atsparūs ilgam laikymui ir, kad juos po to praskiedus, galima būtų gauti vandeninius homogeninius tam tikrą laiko tarpą mišinius, kuriuos galima išpurkšti Įprasta purškimo aparatūra. Mišiniai gali turėti iki 95 svorio %, formos, kuriose yra didelė ir geriau 10-85 svorio % pavyzdžiui, 25-60 svorio % aktyvaus komponento. Praskiestas vandeninis mišinys gali turėti skirtingus aktyvaus komponento kiekius, priklausomai nuo tikslo ir ta aktyvaus komponento koncentracija šiame mišinyje gali sudaryti 0,0005 svorio % arba 0,01-10 svorio %.Aqueous dispersions or emulsion formulations are usually prepared in a concentrated concentration of the active component by diluting the concentrate with water before use. These mixtures must be resistant to prolonged storage and be diluted subsequently to form aqueous homogeneous mixtures for a period of time which may be sprayed by conventional spraying equipment. Mixtures may contain up to 95% by weight of the active ingredient in forms having a high and preferably 10-85% by weight, for example 25-60% by weight. The diluted aqueous mixture may contain different amounts of the active ingredient depending on the purpose and the concentration of the active ingredient in the mixture may be 0.0005% by weight or 0.01-10% by weight.

Šio išradimo kompozicijos gali turėti savo sudėtyje kitų biologiškai aktyvių junginių, pavyzdžiui, junginių, pasižyminčių analogišku arba papildomu fungicidiniu efektytvumu arba augimo reguliavimo, herbicidinių ar insekticidiniu efektyvumu.The compositions of the present invention may contain other biologically active compounds, for example compounds having analogous or complementary fungicidal efficacy or growth control, herbicidal or insecticidal activity.

Fungicidinis junginys, esantis šio išradimo kompozicijoje, gali pasižymėti efektyvumu, slopinant javų (pavyzdžiui, kviečių) varpų ligas, kaip Septoria, Gibberella ir Helminthosporium spp., sėklų ir dirvožemio ligas, apgaulingą ir tikrą vynuogių milteni, obuolių milteni ir rauples, ir kt. Įvedus papildomą fungicidą, kompozicijos efektyvumo spektras gali būti platesnis, negu vieno (I) formulės junginio. Papildomi fungicidai gali turėti sinergistinį poveikį fungicidiniam (I) formulės junginio aktyvumui. Papildomai Įvedamų i šio išradimo kompoziciją fungicidiniu junginių pavyzdžiai apima tetrakonazolą, (RS)-1-aminopropilfosforo rūgšti, (RS)-4-(4-chlorfenil)-2-fenil-2-(1H1,2,4-triazol-l-ilmetii)butironitrilą, (RS)-4-chlor-N(ciano(etoksi)metil)benzamidą, (Z)-N-but-2-eniloksi-metil-2-chlor-2',6'-dietilacetanilidą, 1- (2-ciano-2-metoksiiminoacetil)-3-etil-karbamidą, 1-|(2RS,4RS;2RS,The fungicidal compound present in the composition of the present invention may be effective in inhibiting cereal (e.g. wheat) bean diseases such as Septoria, Gibberella and Helminthosporium spp., Seed and soil diseases, deceptive and true grape mildew, apple mildew and pox. When an additional fungicide is introduced, the composition may have a broader spectrum of efficacy than a single compound of formula (I). The additional fungicides may have a synergistic effect on the fungicidal activity of the compound of formula (I). Further examples of fungicidal compounds to be included in the composition of the present invention include tetraconazole, (RS) -1-aminopropylphosphoric acid, (RS) -4- (4-chlorophenyl) -2-phenyl-2- (1 H -1,2,4-triazol-1-one). ilmetii) butyronitrile, (RS) -4-chloro-N (cyano (ethoxy) methyl) benzamide, (Z) -N-but-2-enyloxy-methyl-2-chloro-2 ', 6'-diethylacetanilide, (2-cyano-2-methoxyiminoacetyl) -3-ethylurea, 1- (2RS, 4RS; 2RS,

4RS)-4-brom-3-(2,4-dichlorofenil)tetrahidrofurfuril|1H-1,2,4-triazolą,3-(2,4-dichlorfenil)-2-(1H-1,2,4triazol-l-il)chinazolin-4(3H)-onas, 3-chlor-4-|4-metil2(1H-1,2,4-triazol-l-metil)-1,3-dioksolan-2-il1 fenil4-chlorfenilo eteris, 4-brom-2-ciano-N,N-dimetil-6-trifluormetilbenzimidazol-l-sulfonamidą, 4-chlorbenzil-N(2,4-dichlorfenil)-2-(1H-1,2,4-triazol-l-il)tioacetamidą, 5-etil-5,8-dihidro-8-okso-(1,3)-dioksalo(4,5-g) chinolin-7-karboninę rūgštį, α-|N-(3-chlor-2, 6-ksilil) 2-metoksiacetamido|-γ-butirolaktoną, anilaziną, BAS 454, benalaksinlą, benomilą, biloksazolą, binaprakrilą, bitertanolą, blasticidiną s, bupirimatą, butiobatą, kaptefolą, kaptaną, karbendazimą, karboksiną, chlorbenztiazoną, chloronebą, chlorotalonilą, chlorozolinatą, junginius kuriuose yra vario, tokius kaip vario oksichloridą, vario sulfatą ir bordo skystį, chlorheksimidą, cimoksonilą, ciprokonazolą, ciprofuramą, di2-piridinilsulfid-1,1'-dioksidą, dichlorfluanidą, dichloną, diklobutrazolą, diklomeziną, dikloraną, dimetamorfą, dimetirimolą, dinikomazolą, dinokapą, ditalimfosą, ditianoną, dodemorfą, dodiną, edifenfosą, etakonazolą, etirimolą etil(Z)-N-benzil-N-(|metil(metiltioetillidenamino-oksikarbonil)amino|tio)-β-alaninatą, fenapanilą, fenarimolą, fenfuramą, fenpiklonilą, fenpropidiną, fenpropimorfą, fentinacetatą, fentinhidroksidą, fentolanilą, flutriafolą, fluzilazolą, folpetą fozetilaliuminį, fuberidazolą furalaksilą, furkonazolącis, kvazatiną, heksakonazolą, imazalilą, iprobenfosą, iprodioną, izoprotiolaną, kasugamiciną, mankozebą, manebą, mepronilą, metalaksilą, metfuroksamą, metsulfovaksą, miklobutanilą, N-(4-metil-6-prop-l-inilpirimidin-2-il)-aniliną, neoazoziną, nikelio dimetilditiokarbamatą, nitrotalizopropilą, nuarimolą, ofuracą, gyvsidabrio organinius junginius, oksadiksilą, oksikarboksilą, oksikarboksiną, penkonazolą, pencikuroną, pefurazoatą, fenozinoksidą, ftalidą, polioksiną D, poliramą, probenazolą, prochloraną, procimidoną, propamokarbą, propikonazoką, propinebą,protiokarbą, pirifenoksą, pirochiloną, piroksifurą, chinometionatą, chintozeną, streptomiciną, sierą, techloftalamą, teknazoną, tebukonazolą, tiabendazolą, tiofanatmetilą, tiramą, tolklofos-metilą,4RS) -4-Bromo-3- (2,4-dichlorophenyl) tetrahydrofurfuryl-1H-1,2,4-triazole, 3- (2,4-dichlorophenyl) -2- (1H-1,2,4-triazol-1) -yl) quinazolin-4 (3H) -one, 3-chloro-4- [4-methyl-2 (1H-1,2,4-triazol-1-methyl) -1,3-dioxolan-2-yl] phenyl4-chlorophenyl ether, 4-bromo-2-cyano-N, N-dimethyl-6-trifluoromethylbenzimidazole-1-sulfonamide, 4-chlorobenzyl-N- (2,4-dichlorophenyl) -2- (1H-1,2,4-triazole- 1-yl) thioacetamide, 5-ethyl-5,8-dihydro-8-oxo- (1,3) -dioxal (4,5-g) quinoline-7-carboxylic acid, α- N - (3-chloro) -2, 6-xylyl) 2-methoxyacetamide,? -Γ-butyrolactone, anilazine, BAS 454, benalaxinil, benomyl, biloxazole, binapracryl, bitertanol, blasticidine s, bupirimate, butiobate, captefol, captanone, carbendazon, carbendazim, chlorothalonil, chlorozolinate, compounds containing copper, such as copper oxychloride, copper sulfate and burgundy, chlorheximide, cymoxonyl, ciproconazole, ciprofuram, di2-pyridinylsulfide-1,1'-dioxide, dichlorfluanid, dichlone, butrazole, diclomezine, dichlorane, dimetamorph, dimethirimol, dicinazazole, dinocap, ditalymphos, dithianone, dodemorph, dodine, edifenphos, etaconazole, etirimol ethyl (Z) -N-benzylthio-n-methylamino-thio (methyl) -ethylamino] -β-alaninate, fenapanilą, fenarimol fenfuramą, fenpiclonil, fenpropidin, fenpropimorph, fentinacetatą, fentinhidroksidą, fentolanilą, flutriafol, fentin hydroxide, fozetilaliuminį folpet, fuberidazole furalaxyl, furkonazolącis, guazatine, hexaconazole, imazalil, iprobenfos, iprodione, isoprothiolane, kasugamycin, maneb , maneb, mepronil, metalaxyl, metfuroxam, metsulfovax, myclobutanyl, N- (4-methyl-6-prop-1-inylpyrimidin-2-yl) -aniline, neoazosin, nickel dimethyldithiocarbamate, nitrotalisopropyl, nuarimol, ofuracole, ofuracol, oxadixyl, oxycarboxyl, oxycarboxin, penconazole, pencicuron, pefurazoate, phenosynoxide, phthalide, polyoxin D, polira probenazole, prochlorane, procymidone, propamocarb, propiconazoc, propineb, prothiocarb, pirifenox, pyrochylone, piroxifur, quinomethionate, chintozene, streptomycin, sulfur, techlophthalam, techazone, tebuconazole, tebuconazole,

1,1'-iminodi(oktametilen)-diąuanidino triacetato druską, triadimefoną, triadimefoną, triadimenolą, triazbutilą, triciklazolą, tridemorfą, triforiną, validamiciną A, pirazofosą, pirolnitriną, vinklozoliną ir zinebą. (I) formulės junginius galima sumaišyti su dirva, puvenomis ar kita šaknų aplinka, apsaugant augalus nuo sėklų, dirvos ar lapų grybelinių susirgimų.1,1'-iminodi (octamethylene) -diauanidine triacetate salt, triadimefon, triadimefon, triadimenol, triazbutyl, tricyclazole, tridemorph, triforin, validamycin A, pyrazophos, pyrrolitrin, vinclozoline and zineb. The compounds of formula (I) may be admixed with soil, rot or other root media to protect the plants from fungal diseases of seed, soil or leaves.

Tinkami insekticidai, kuriuos galima įjungti į šio išradimo kompoziciją apima: buprofeziną, karbanilą, karbofuraną, karbosulfaną, chlorpirifosą, cikloprotriną, demeton-s-metilą, diazinoną, dimetoatą, etofenproksą, fenitrotioną, fenobukarbą, fentioną, formotioną, izoprokarbą, izoksationą, monokrotofasą, fentoatą, pirimikarbą, propafosą ir XMC.Suitable insecticides which may be included in the composition of the present invention include: buprofezin, carbanyl, carbofuran, carbosulfan, chlorpyrifos, cycloprotrine, demeton-s-methyl, diazinon, dimethoate, ethofenprox, fenitrothion, phenobucarbo, fenthion, formo phentate, pirimicarb, propafos and XMC.

Augalų augimo reguliatoriai yra junginiai, naikinantys piktožes arba susiformavusias jų sėklų galvutes, arba selektyviai slopinantys nereikalingų augalų augimą (pavyzdžiui, žoles).Plant growth regulators are compounds that kill the angiosperms or their seed heads or selectively inhibit the growth of redundant plants (such as grasses).

Augalų augimo reguliatoriai, naudojami su šio išradimo junginiais, apima:Plant growth regulators used with the compounds of the present invention include:

3,6-dichlorpikolino rūgštį, 1-(4-chlorfenil)-4,6-dimetil-2-okso-l,2-dihidropiridin-3-karboninę rūgštį, metil-3,6-dichloranizatą, abscizinę rūgštį, azulaną, benzoilprop-etilą, karbetamidą, daminozidą, difenzokvatą, dikegulaką, etefoną, fenpentezolą, fluoridamidą, glifozatą, glifoziną, hidroksibenzonitrilus (pavyzdžiui, bromoksinilą), inabenfidą, izopirimolą, ilgos grandinės riebiuosius alkoholius ir rūgštis, maleinhidrasidą, melfluididą, morfaktinus (pavyzdžiui, chlorfluoroekolą), fenoksiacto rūgštis (pavyzdžiui, 2,4-D arba MCPA), paklobutrazolą, pakeistą benzoinę rūgštį (pavyzdžiui, trijodobenzoinę rūgštį), pakeistus ketvirtinius amonio ir fosfonio junginius (pavyzdžiui, chlormekvatą, chlorfonijų arba mepikvatchloridą), teknazeną, auksinus (pavyzdžiui, indolacto rūgštį, indolburirinė rūgštis, naftilacto rūgštis arba naftoksiacto rūgštis) , citokininus (pavyzdžiui, benzimidazolą, benziladeniną, benzilaminopuriną, difenilkarbamidą arba kinetinę), giberelinus (pavyzdžiui, GA3, GA4 arba GA7) ir triapentenolą.3,6-dichloropicolinic acid, 1- (4-chlorophenyl) -4,6-dimethyl-2-oxo-1,2-dihydropyridine-3-carboxylic acid, methyl 3,6-dichloroanisate, abscisic acid, azulan, benzoylprop -ethyl, carbetamide, daminozide, difenzoquate, dicegulac, ethephon, fenpentezole, fluoramidamide, glyphosate, glyphosine, hydroxybenzonitriles (e.g. phenoxyacetic acid (e.g. 2,4-D or MCPA), paclobutrazole, substituted benzoic acid (e.g. triiodobenzoic acid), substituted quaternary ammonium and phosphonium compounds (e.g. , indolburic acid, naphthylacetic acid or naphthoxyacetic acid), cytokinins (e.g. benzimidazole, benzyladenine, benzylaminopurine, urea or kinetic), gibberellins (e.g. GA 3 , GA 4 or GA 7 ) and triapentenol.

azoto atmosferoje,in a nitrogen atmosphere,

Išradimas iliustruojamas žemiau pateiktais pavyzdžiais. Pavyzdžiuose terminas eteris reiškia dietilo eterį, tirpalų džiovinimui naudojamas magnio sulfatas, o tirpalai koncentruojami sumažintame slėgyje. Reakcijos su jautriais vandeniui tarpiniais junginiais vykdomos > tirpikliai naudojimą. Pateikti duomenys selektyvūs, absorbcijas visais išdžiovinami prieš spindulių ir BMR nebuvo norima pateikti visas atvejais. Išskyrus specialiai nurodytus atvejus, IR-BMR spektrai buvo užrašomi CDC13 tirpale.The invention is illustrated by the following examples. In the examples, the term ether refers to diethyl ether, magnesium sulfate is used to dry solutions, and the solutions are concentrated under reduced pressure. Reactions with water-sensitive intermediates are carried out using solvents. The data presented is selective, the absorbances were all dried before radiation, and NMR was not intended to be reported in all cases. Except as specifically provided otherwise, the IR-NMR spectra were recorded CDC1 3 solution.

infraraudonųinfrared

Toliau naudojami tokie sutrumpinimai:The following abbreviations are used below:

THF - tetrahidrofuranas;s - singletasTHF - tetrahydrofuran, s - singlet

DMF - N,N-dimetilformamidas;d - dubletasDMF - N, N-dimethylformamide, d - doublet

BMR - branduolinis magnetinis rezonansas;t tripletas m - multipletasNMR - nuclear magnetic resonance; t triplet m - multiplet

IR - infraraudonų spindulių spektroskopija;p platus kv - kvartetasIR - infrared spectroscopy; p broad kv - quartet

Lyd.t. - lydymosi temperatūraMelting point - melting point

PavyzdysAn example

2-Chlor-4-(2',2'-dimetilpropionamido)-N,N-dimetilbenzamido (5 junginys 1 lentelėje) gavimasPreparation of 2-Chloro-4- (2 ', 2'-dimethylpropionamide) -N, N-dimethylbenzamide (Compound 5 in Table 1)

StadijaStage

2-Chlor-4-nitro-N,N-dimetilbenzamido gavimasPreparation of 2-Chloro-4-nitro-N, N-dimethylbenzamide

25,0 g 2-chlor-4-nitrobenzoinės rūgšties 3 vai. virinama su grįžtamu šaldytuvu 80 g tionilchlorido su keliais lašais DMF. Po to tionilo chlorido perteklius nugarinamas ir nešvarus 2-chlor-4-nitrobenzoilchloridas sulašinamas į 70 ml 40% vandeninio dimetilamino 0-5°C temperatūroje. Reakcijos mišinys 0,5 vai. maišomas, po to iškritę geltoni kristalai nufiltruojami, perplaunami vandeniu, išdžiovinami ir gaunama 24,7 g gelsvų kristalų, lyd.t. 116-117°C.25.0 g of 2-chloro-4-nitrobenzoic acid for 3 hours. reflux 80 g of thionyl chloride with a few drops of DMF. The excess thionyl chloride is then evaporated off and the crude 2-chloro-4-nitrobenzoyl chloride is added dropwise to 70 ml of 40% aqueous dimethylamine at 0-5 ° C. Reaction mixture 0.5 h. After stirring, the yellow crystals are filtered off, washed with water, dried to give 24.7 g of yellow crystals, m.p. 116-117 ° C.

BMR (CDC13, 90 MHz) δ : 2,90(3H,s), 3,20(3H,s),NMR (CDCl 3 , 90 MHz) δ: 2.90 (3H, s), 3.20 (3H, s),

7,49(lH,d), 8,12(lH,d), 8,27(lH,m).7.49 (1H, d), 8.12 (1H, d), 8.27 (1H, m).

IR (nujolas) : 3100, 1640 cm1.IR (nujol): 3100, 1640 cm @ -1 .

StadijaStage

4-Amino-2-chlor-N,N-dimetilbenzamido gavimasPreparation of 4-Amino-2-chloro-N, N-dimethylbenzamide

10,0 g geležies miltelių (prieš tai redukuoti vandeniu) suspenduojama 80 ml etanolio ir 10 ml vandens ir intensyviai maišant, pridedama 4 ml koncentruotos druskos rūgšties. Per 15 min. nedidelėmis porcijomis pridedama 7,50 g 2-chlor-4-nitro-N,N-dimetilbenzamido ir mišinys 5 vai. kaitinamas 50-60°C temperatūroje maišant. Mišinys filtruojamas per ceolitą, o etanolis išgarinamas. Pridedama 200 ml vandens ir 20 ml koncentruotos druskos rūgšties, reakcijos mišinys praplaunamas etilacetatu ir po to pašarminamas natrio bikarbonatu iki pH 8, ir ekstrahuojamas metilenchloridu. Organiniai ekstraktai išdžiovinami ir išgarinami, gaunant 5,21 g pilkų kristalų, kurie perkristalizuojami iš chloroformo/etilacetato mišinio, gaunant 3,46 g baltų kristalų (lyd.t. 170-173°C) .10.0 g of iron powder (previously reduced with water) are suspended in 80 ml of ethanol and 10 ml of water and 4 ml of concentrated hydrochloric acid are added with vigorous stirring. Within 15 minutes 7.50 g of 2-chloro-4-nitro-N, N-dimethylbenzamide are added in small portions and the mixture is stirred for 5 hours. heated at 50-60 ° C with stirring. The mixture is filtered through zeolite and the ethanol is evaporated. 200 ml of water and 20 ml of concentrated hydrochloric acid are added, the reaction mixture is washed with ethyl acetate and then basified to pH 8 with sodium bicarbonate and extracted with methylene chloride. The organic extracts were dried and evaporated to give 5.21 g of gray crystals which were recrystallized from chloroform / ethyl acetate to give 3.46 g of white crystals (m.p. 170-173 ° C).

BMR (CDC13, 270 MHz) δ : 2,89 (3H,s), 3,ll(3H,s),NMR (CDCl 3 , 270 MHz) δ: 2.89 (3H, s), 3.11 (3H, s),

3,87(2H,bs), 6,57(lH,dd), 6,67(lH,s), 7,07(lH,d).3.87 (2H, bs), 6.57 (1H, dd), 6.67 (1H, s), 7.07 (1H, d).

IR (skysta plėvelė) : 3440-3340, 1640 cm1.IR (liquid film): 3440-3340, 1640 cm @ -1 .

StadijaStage

2-Chlor-4(2',2'-dimetilpropionamido)-N,Ndimetilbenzamido gavimasPreparation of 2-Chloro-4 (2 ', 2'-dimethylpropionamide) -N, N-dimethylbenzamide

1,0 g 4-amino-2-chlor-N,N-dimetilbenzamido ir 1,21 g trietilamino ištirpinama 20 ml metilenchlorido ir tirpalas atšaldomas iki 0-5°C. Į mišinį sulašinamas 1,21 g 2,2-dimetilpropionilchlorido tirpalas, palaikant temperatūrą žemiau 10°C, o gautas oranžinis tirpalas 0,5 vai. maišomas 0-10°C temperatūroje. Po to organinis tirpalas praplaunamas vandeniniu natrio bikarbonato po to vandeniu, džiovinamas, išgarinamas ir kitas oranžinis produktas. Jis perkristalichloroformo mišinio (3:1), tirpalu, gaunamas zuoj amas iš etilacetato:Dissolve 1.0 g of 4-amino-2-chloro-N, N-dimethylbenzamide and 1.21 g of triethylamine in 20 ml of methylene chloride and cool to 0-5 ° C. A solution of 1.21 g of 2,2-dimethylpropionyl chloride is added dropwise to the mixture at a temperature below 10 [deg.] C., and the resulting orange solution is treated with 0.5 h. stirred at 0-10 ° C. The organic solution is then washed with aqueous sodium bicarbonate followed by water, dried, evaporated and the other orange product. It is recrystallized from a solution of a mixture of chloroform (3: 1) in ethyl acetate:

gaunant 1,027 g beveik baltų kristalų, lyd.t. 202203°C.yielding 1.027 g of off-white crystals, m.p. 202203 ° C.

BMR (CDC13, 270 MHz) (3H,s), 7,16(lH,d), (lH,bs) .NMR (CDCl 3 , 270 MHz) (3H, s), 7.16 (1H, d), (1H, bs).

δ l,32(9H,s), 2,86(3H,s), 3,13δ 1.32 (9H, s), 2.86 (3H, s), 3.13

7,34(lH,d), 7,68(lH,s), 7,727.34 (1H, d), 7.68 (1H, s), 7.72

IR (nujolas): 3340, 1690, 1630 cmIR (nujol): 3340, 1690, 1630 cm

PavyzdysAn example

2-Chlor-4(2'-metilpropionamido)-N,N-dietilbenzamido gavimas (1 junginys 1 lentelėje)Preparation of 2-Chloro-4 (2'-methylpropionamide) -N, N-diethylbenzamide (Compound 1 in Table 1)

StadijaStage

2-Chlor-4-(2'-metilpropionamido)benzoinės rūgšties gavimas ml 4-amino-2-chlorbenzoinės rūgšties 60 ml vandens ir 25 ml 1,2-dimetoksietano maišoma su 5,04 g natrio bikarbonato ir ruda suspensija atšaldoma iki 0-5°C. Energingai maišant, per 10 min. sulašinama 4,26 g 2metilpropionilchlorido ir mišinys 2 vai. maišomas 010°C temperatūroje. Mišinys išpilamas į 2M HCl rūgštį, o rusvos nuosėdos praplaunamos vandeniu, filtruojamos, džiovinamos, gaunant 6,30 g šviesiai rudų kristalų, lyd.t. 206-209°C.Preparation of 2-Chloro-4- (2'-methylpropionamide) benzoic acid A solution of 4-amino-2-chlorobenzoic acid in ml of water and 25 ml of 1,2-dimethoxyethane was mixed with 5.04 g of sodium bicarbonate and cooled to 0- 5 ° C. With vigorous stirring, within 10 min. 4.26 g of 2-methylpropionyl chloride are added dropwise and the mixture is stirred for 2 hours. stirred at 010 ° C. The mixture was poured into 2M HCl and the brownish precipitate was washed with water, filtered, dried to give 6.30 g of light brown crystals, m.p. 206-209 ° C.

BMR(d6DMSO, 270 MHz) δ : l,05(6H,d), 2,53(1H, septetas), 7,51(lH,dd), 7,78(lH,d), 7,86(lH,s), 14-12(1H, labai ps) .NMR (d 6 DMSO, 270 MHz) δ: 1.05 (6H, d), 2.53 (1H, septet), 7.51 (1H, dd), 7.78 (1H, d), 7.86 (1H, s), 14-12 (1H, very ps).

IR (nujolas) : 3320, 1705, 1670 cm1.IR (nujol): 3320, 1705, 1670 cm @ -1 .

StadijaStage

2-Chlor-4-(2'-metilpropionamido)benzoilchlorido gavimasPreparation of 2-Chloro-4- (2'-methylpropionamide) benzoyl chloride

0,63 g oksalilchlorido 5 ml sauso THF per 5 min.0.63 g of oxalyl chloride in 5 mL of dry THF over 5 min.

sumaišoma su 1,0 g benzoinės rūgšties 5 temperatūroje. Po tomixed with 1.0 g of benzoic acid at 5 ° C. Then

2-chlor-4-(2'-metilpropionamido) ml sauso THF tirpalo kambario pridedamas 1 lašas sauso DMF, kuris iššaukia energingą dujų išsiskyrimą ir mišinys šiek tiek sušyla. Maišoma 4 vai., o po to pridedamas dar vienas DMF lašas, o THF išgarinamas, gaunant klampią rudą dervą, kuri toliau naudojama be valymo.To 2-chloro-4- (2'-methylpropionamide) ml dry THF solution room add 1 drop of dry DMF which causes vigorous evolution of gas and slightly warm the mixture. After stirring for 4 hours, a further drop of DMF is added and the THF is evaporated to give a viscous brown gum which is used without further purification.

IR (skysta plėvelė): 3320, 3260, 3160, 3070, 1780,IR (liquid film): 3320, 3260, 3160, 3070, 1780,

1710, 1680, cm'1.1710, 1680, cm -1 .

StadijaStage

2-Chlor-4(2’-metilpropionamido)-N,N-dietilbenzamido gavimasPreparation of 2-Chloro-4 (2'-methylpropionamide) -N, N-diethylbenzamide

Prieš tai einančioje stadijoje gautas nešvarus 2-chlor4-(2’-metilpropionamido)benzoilchloridas 10-tyje ml sauso THF per 10-15 min. maišant sulašinamas i 1,46 g dietilamino tirpalą 10 ml sauso THF 0-5°C temperatūroje. Maišoma 0-10°C temperatūroje, po to reakcijos mišinys laikomas per išpilamas i šaltą temperatūroje, ekstrahuoj amas išgarinamas ir naktį kambario vandeni ir etilacetatu. Ekstraktas išdžiovinamas, gaunama klampi derva, kuri lėtai kristalizuojasi ir kuri po to perkristalinama iš etilacetato, gaunant 0,507 g baltų kristalų.The preceding step gave the crude 2-chloro-4- (2'-methylpropionamide) benzoyl chloride in 10 mL of dry THF over 10-15 min. while stirring, dropwise add a solution of 1.46 g of diethylamine in 10 ml of dry THF at 0-5 ° C. After stirring at 0 to 10 ° C, the reaction mixture is kept under reflux, extracted with water and ethyl acetate overnight. The extract is dried to give a viscous gum which is slowly crystallized and then recrystallized from ethyl acetate to give 0.507 g of white crystals.

BMR (CDC13, 270 MHz), δ : l,04(3H,t), l,21(6H,d), 1,26 (3H,t), 2,58(1H,septetas), 3, 15(2H,kv), 3,39(1H, pm) ,NMR (CDCl 3 , 270 MHz), δ: 1.04 (3H, t), 1.21 (6H, d), 1.26 (3H, t), 2.58 (1H, septet), 3, 15 (2H, kv), 3.39 (1H, pm),

3,74(lH,pm), 7,04(lH,d), 7,30(lH,dd), 7,51(lH,s),3.74 (1H, pm), 7.04 (1H, d), 7.30 (1H, dd), 7.51 (1H, s),

8,58 (1H,ps) .8.58 (1H, ps).

IR (nujolas): 3300, 3250, 3165, 1685 cm1.IR (nujol): 3300, 3250, 3165, 1685 cm @ -1 .

PavyzdysAn example

1- |3'-Chlor-4'-(N,N-dimetilkarbamoil)fenilĮ-3,3dimetilazetidin-2-ono gavimas (11 junginys 1 lentelėje)Preparation of 1- [3'-Chloro-4 '- (N, N-dimethylcarbamoyl) phenyl] -3,3-dimethylazetidin-2-one (Compound 11 in Table 1)

StadijaStage

2-Chlor-4-(3'-chlor-2',2'-dimetilpropionamido)-N,Ndimetilbenzamido gavimasPreparation of 2-Chloro-4- (3'-chloro-2 ', 2'-dimethylpropionamide) -N, N-dimethylbenzamide

1,86 g 3-chlor-2,2-dimetilpropionilchlorido maišant sulašinama per 5 min. i, 2,00 g 4-amino-2-chlor-N, Ndimetilbenzamido, suspenduoto sausame metilenchloride (40 ml) ir sausame trietilamine (1,21 g), palaikant temperatūrą žemiau 10°C 1 vai. maišoma ir mišinys pašildomas iki kambario temperatūros, po to pridedama 40 ml metilenchlorido, o tirpalas praplaunamas 2M HCl, sočiu vandeniniu natrio bikarbonato tirpalu, o po to sočiu druskos tirpalu. Tirpalas džiovinamas, išgarinamas ir gaunamas lipnus geltonas kietas junginys, kuris perkristalizuojamas iš etilenacetato/chloroformo mišinio, gaunant 2,349 g balto kieto kristalinio junginio, lyd.t. 179-181°C.1.86 g of 3-chloro-2,2-dimethylpropionyl chloride are added dropwise with stirring over 5 minutes. 2.00 g of 4-amino-2-chloro-N, N-dimethylbenzamide suspended in dry methylene chloride (40 ml) and dry triethylamine (1.21 g) were maintained at a temperature below 10 ° C for 1 h. After stirring and warming to room temperature, 40 ml of methylene chloride are added and the solution is washed with 2M HCl, saturated aqueous sodium bicarbonate solution, and then with brine. The solution is dried, evaporated to give a sticky yellow solid which is recrystallized from ethylene acetate / chloroform to give 2.389 g of a white solid crystalline compound, m.p. 179-181 ° C.

BMR (CDC13, 270 MHZ), δ : l,42(6H,s), 2,86(3H,s),NMR (CDCl 3 , 270 MHZ), δ: 1.42 (6H, s), 2.86 (3H, s),

3,14(3H,s), 3,73(2H,s), 7,06(lH,d), 7,26(lH,dd),3.14 (3H, s), 3.73 (2H, s), 7.06 (1H, d), 7.26 (1H, dd),

7,50(1H,s), 8,48(lH,ps).7.50 (1H, s), 8.48 (1H, ps).

IR (nujolas): 3310, 1670, 1620 cm1.IR (nujol): 3310, 1670, 1620 cm @ -1 .

StadijaStage

1-|3'-Chlor-4'-(N,N-dimetilkarbamoil)fenil| -3,3dimetilazetidin-2-ono gavimas1- [3'-Chloro-4 '- (N, N-dimethylcarbamoyl) phenyl] Yielding -3,3-dimethylazetidin-2-one

4,00 g natrio hidroksido ir 0,10 g tetrabutilamonio bromido 10 ml vandens tirpalas supilamas d, 1,00 g 2chlor-4-(3'chlor-chlor-2',2'-dimetilpropionamido)-N, Ndimetilbenzamido 10 ml metilenchlorido suspensiją ir dvifazinė sistema 1 vai. tūroje. Po to pridedama metilenchlorido ir visas maišoma kambario tempera10 ml vandens ir 10 ml metilenchlorido sluoksnis praplaunamas druskos tirpalu, džiovinamas, išgarinamas, gaunant gelsvą kietą junginį. Jis perkristalizuoj amas iš etilacetato/heksano mišinio, gaunant 0,516 g balto kristalinio kieto junginio, lyd.t. 122-123°C.A solution of 4.00 g of sodium hydroxide and 0.10 g of tetrabutylammonium bromide in 10 ml of water is added d, 1.00 g of 2-chloro-4- (3'-chloro-chloro-2 ', 2'-dimethylpropionamide) -N, N-dimethylbenzamide in 10 ml of methylene chloride suspension and biphasic system for 1 hour. in volume. Methylene chloride is then added and the whole is stirred at room temperature in 10 mL of water and the 10 mL of methylene chloride is washed with brine, dried, evaporated to give a yellowish solid. It was recrystallized from ethyl acetate / hexane to give 0.516 g of a white crystalline solid, m.p. 122-123 ° C.

BMR (CDC13, 270 MHz) δ : l,42(6H,s), 2,87(3H,s),NMR (CDCl 3 , 270 MHz) δ: 1.42 (6H, s), 2.87 (3H, s),

3,13(3H,s), 3,46(2H,s), 7,27(2H,t), 7,39(lH,s).3.13 (3H, s), 3.46 (2H, s), 7.27 (2H, t), 7.39 (1H, s).

IR (nujolas) : 3600-3100, 1740, 1625 cm1.IR (nujol): 3600-3100, 1740, 1625 cm @ -1 .

PavyzdysAn example

2-metoksi-4-(2',2'-dimetilpropionamido)-N,Ndimetilbenzamido (1 junginio II lentelėje) gavimasPreparation of 2-methoxy-4- (2 ', 2'-dimethylpropionamide) -N, N-dimethylbenzamide (Compound 1 in Table II)

StadijaStage

Metil-2-metoksi-4-(2 ', 2 '-dimetilpropionamido)benzoato gavimasPreparation of methyl 2-methoxy-4- (2 ', 2'-dimethylpropionamide) benzoate

3,03 g metil-2-metoksi-4-aminobenzoato ir 1,83 g trietilamino 0-5°C temperatūroje maišoma 50-tyje ml metilenchlorido. Į ši tirpalą sulašinama 6,07 g 2,2dimetilpropionilchlorido 10-tyje ml sauso metilenchlorido. Mišinys maišomas per naktį kambario temperatūroje ir išpilamas į praskiestą HCl. Organinis sluoksnis atskiriamas, praplaunamas praskiestu vandeniniu natrio bikarbonatu ir po to vandeniu, džiovinamas, išgarinamas ir gauna besikristalizuojančią alyvą. Produktas kaitinamas su heksanu, filtruojamas ir gaunama 3,61 g balto kieto junginio.3.03 g of methyl 2-methoxy-4-aminobenzoate and 1.83 g of triethylamine are stirred in 50 ml of methylene chloride at 0-5 ° C. To this solution is added dropwise 6.07 g of 2,2-dimethylpropionyl chloride in 10 ml of dry methylene chloride. The mixture was stirred overnight at room temperature and poured into dilute HCl. The organic layer was separated, washed with dilute aqueous sodium bicarbonate followed by water, dried, evaporated to give a crystallizing oil. The product was heated with hexane, filtered to give 3.61 g of a white solid.

δ : l,33(9H,s), 3,86(3H,s), 3,94δ: 1.33 (9H, s), 3.86 (3H, s), 3.94

7,45(lH,s), 7,79(lH,d), 7,827.45 (1H, s), 7.79 (1H, d), 7.82

BMR(CDC13, 270 MHz), (3H,s), 6,79(lH,dd) (lH,d) .NMR (CDCl 3 , 270 MHz), (3H, s), 6.79 (1H, dd) (1H, d).

StadijaStage

2-Metoksi-4-(2 ’, 2 ’-dimetilpropionamido)benzoinės rūgšties gavimasPreparation of 2-methoxy-4- (2 ', 2' -dimethylpropionamide) benzoic acid

2,98 g metil-2-metoksi-4-(2’, 2'-dimetilpropionamido) benzoato kambario temperatūroje 3 vai. maišoma su 0,725 g kalio hidroksido 50-tyje ml metanolio, po to 8 vai. virinama su grįžtamuoju šaldytuvu ir išpilama į vandenį. Mišinys ekstrahuojamas etilacetatu ir parūgštinamas HCl. Parūgštinta frakcija ekstrahuojama etilacetatu, ekstraktas džiovinamas, išgarinamas ir gaunama 1,24 g kieto produkto.2.98 g of methyl 2-methoxy-4- (2 ', 2'-dimethylpropionamide) benzoate at room temperature for 3 hours. mixed with 0.725 g of potassium hydroxide in 50 ml of methanol, then for 8 hours. boil under reflux and pour into water. The mixture was extracted with ethyl acetate and acidified with HCl. The acidified fraction was extracted with ethyl acetate, and the extract was dried, evaporated to give 1.24 g of a solid.

BMR (CDC13, 270 MHz), δ : l,36(9H,s), 4,10(3H,s),NMR (CDCl 3 , 270 MHz), δ: 1.36 (9H, s), 4.10 (3H, s),

6,78(lH,dd), 8,10(2H,m), 10,61(lH,s).6.78 (1H, dd), 8.10 (2H, m), 10.61 (1H, s).

StadijaStage

2-Metoksi-4-(2',2'-dimetilpropionamido)benzoilchlorido gavimasPreparation of 2-methoxy-4- (2 ', 2'-dimethylpropionamide) benzoyl chloride

Į 1,04 g maišomos 2-metoksi-4-(2',2'-dimetilpropionamido) benzoinės rūgšties 25-iuose ml sauso eterio kambario temperatūroje sulašinama 1,4 g oksachlorido 5iuose ml sauso eterio, esant DMF pėdsakams. Po to mišinys 4 vai. maišomas ir paliekamas nakčiai. Pridedama metilenchlorido ir mišinys išgarinamas, gaunant 1,12 g geltono kieto chloranhidrido.To 1.04 g of stirring 2-methoxy-4- (2 ', 2'-dimethylpropionamide) benzoic acid in 25 ml of dry ether is added dropwise 1.4 g of oxachloride in 5 ml of dry ether in traces of DMF. The mixture is then stirred for 4 hours. stirred and left overnight. Methylene chloride is added and the mixture is evaporated to give 1.12 g of yellow solid chlorohydride.

StadijaStage

2-Metoksi-4-(2',2'-dimetilpropionamido)-N,Ndimetilbenzamido gavimasPreparation of 2-methoxy-4- (2 ', 2'-dimethylpropionamide) -N, N-dimethylbenzamide

1,12 g 2-metoksi-4-(2',2'-dimetilpropionamido)benzoilchlorido 10-yje ml sauso THF per 30 min. sulašinama į maišomą 1,17 g 40% vandeninį dimetilamino tirpalą 15oje ml THF 0-5°C temperatūroje. Po to mišinys 1 vai. maišomas 5-10°C temperatūroje, laikomas per naktį kambario temperatūroje, išpilamas į vandenį ir ekstrahuojamas etilacetatu. Ekstraktas džiovinamas, išgarinamas ir gaunama 0,889 g kieto geltono produkto, lyd.t. 143-144°C.1.12 g of 2-methoxy-4- (2 ', 2'-dimethylpropionamide) benzoyl chloride in 10 ml of dry THF over 30 min. is added dropwise to a stirred solution of 1.17 g of 40% aqueous dimethylamine in 15 ml of THF at 0-5 ° C. The mixture is then stirred for 1 hour. After stirring at 5-10 [deg.] C., store overnight at room temperature, pour into water and extract with ethyl acetate. The extract was dried, evaporated to give 0.889 g of a solid yellow product, m.p. 143-144 ° C.

BMR (CDC13, 270 MHz) δ : l,33(9H,s), 2,85(3H,s), 3,11 (3H,s), 6,75(lH,dd), 7,15(lH,d), 7,48(lH,s), 7,65 (lH,d) .NMR (CDCl 3 , 270 MHz) δ: 1.33 (9H, s), 2.85 (3H, s), 3.11 (3H, s), 6.75 (1H, dd), 7.15 ( 1H, d), 7.48 (1H, s), 7.65 (1H, d).

PavyzdysAn example

2-Trifluormetil-4-(2',2'-dimetilpropionamido)-N,Ndimetilenbenzamido gavimas (7 junginys II lentelėje)Preparation of 2-Trifluoromethyl-4- (2 ', 2'-dimethylpropionamide) -N, N-dimethylbenzamide (Compound 7 in Table II)

StadijaStage

2-Trifluormetil-4-(2',2’-dimetilpropionamido)benzonitrilo gavimasPreparation of 2-Trifluoromethyl-4- (2 ', 2'-dimethylpropionamide) benzonitrile

3,79 g 2,2-dimetilpropionilchlorido 5 ml sauso metilenchlorido lėtai 0-5°C temperatūroje sumaišoma į 3,02 g 4-ciano-3-trifluormetilamino ir 3,34 g trietilamino 50-yje ml sauso metilenchlorido tirpalą. Po to mišinys 1,5 vai. maišomas kambario temperatūroje ir išpilamas į praskiestą HCl. Organinė frakcija praplaunama praskiestu vandeniniu natrio karbonato tirpalu, po to vandeniu, išdžiovinama ir išgarinama, gaunant oranžinį kietą produktą. Šis perksristalizuojamas ir gaunami geltonos spalvos milteliai.3.79 g of 2,2-dimethylpropionyl chloride are slowly added to a solution of 3.02 g of 4-cyano-3-trifluoromethylamine and 3.34 g of triethylamine in 50 ml of dry methylene chloride at a temperature of 0-5 ° C. The mixture was then stirred for 1.5 hours. stirred at room temperature and poured into dilute HCl. The organic fraction is washed with dilute aqueous sodium carbonate solution, then water, dried and evaporated to give an orange solid. This is recrystallized to give a yellow powder.

BMR (CDCI3, 270 MHz), δ : 1,35(9H, s),NMR (CDCl 3, 270 MHz), δ: 1.35 (9H, s),

7,78(lH,d), 7,93(lH,dd), 8,03(lH,d).7.78 (1H, d), 7.93 (1H, dd), 8.03 (1H, d).

7,61(lH,s),7.61 (1H, s),

StadijaStage

2-Trifluormetil-4-(2',2’-dimetilpropionamido)-benzamido gavimas ml 30% vandeninio vandenilio peroksido ir 8,5 ml 20% vandeninio natrio hidroksido tirpalas supilamas į 5,03 g 2-trifluormetil-4-(2',2'-dimetilpropionamido)-benzonitrilo 140-yje ml etanolio ir reakcijos mišinys 5 dienas maišomas kambario temperatūroje, o per tą laiką papildomai pridedant 100 ml etanolio. Po to reakcijos mišinys 24 vai. kaitinamas 50°C temperatūroje, išpilamas i vandeni ir ekstrahuojamas etilacetatu. Po to organinis sluoksnis džiovinamas, išgarinamas ir gaunama alyva, kuri chromatografuojama per silikagelį, gaunant 2,89 g norimo produkto.Preparation of 2-Trifluoromethyl-4- (2 ', 2'-dimethylpropionamide) -benzamide A solution of 30% aqueous hydrogen peroxide and 8.5 ml of 20% aqueous sodium hydroxide solution was added to 5.03 g of 2-trifluoromethyl-4- (2'). , 2'-dimethylpropionamido) -benzonitrile in 140 mL of ethanol and the reaction mixture was stirred at room temperature for 5 days, during which time 100 mL of ethanol was added. The reaction mixture was then stirred for 24 hours. heated at 50 ° C, poured into water and extracted with ethyl acetate. The organic layer is then dried, evaporated to give an oil which is chromatographed on silica gel to give 2.89 g of the desired product.

BMR (CDC13, 270 MHz) δ : l,35(9H,s), 5,80(2H,ps),NMR (CDCl 3 , 270 MHz) δ: 1.35 (9H, s), 5.80 (2H, ps),

7,54(lH,s), 7,59(lH,d), 7,82(lH,dd), 7,90(lH,d).7.54 (1H, s), 7.59 (1H, d), 7.82 (1H, dd), 7.90 (1H, d).

StadijaStage

2-Trifluormetil-4-(2',2'-dimetilpropionamido)-benzoinės rūgšties gavimas ml koncentruotos HCl supilama į 2,35 g 2trifluormetil-4- (2',2'-dimetilpropionamido)-benzamido 35-iuose ml ledinės acto rūgšties -5-0°C temperatūroje. Po to į mišinį sulašinamas 1,807 g natrio nitrito tirpalas 10-yje ml vandens ir 1 vai. maišoma -5-0°C temperatūroje. Reakcijos mišinys atšaldomas iki kambario temperatūros, 24 vai. maišomas, išpilamas į vandenį ir ekstrahuojamas metilenchloridu. Metilenchlorido frakcija praplaunama praskiestu natrio hidroksido tirpalu ir šarminis parūgštinamas praskiesta HCl. Parūgštintas ekstrahuojamas metilenchloridu, o organinis vandeniniu sluoksnis sluoksnis sluoksnis džiovinamas, produkto.Preparation of 2-Trifluoromethyl-4- (2 ', 2'-dimethylpropionamide) benzoic acid Pour 2.35 g of 2-trifluoromethyl-4- (2', 2'-dimethylpropionamide) benzamide into 35 ml of glacial acetic acid. At -5 to 0 ° C. A solution of 1.807 g of sodium nitrite in 10 ml of water is then added dropwise to the mixture for 1 hour. stirred at -5-0 ° C. The reaction mixture was cooled to room temperature for 24 hours. stirred, poured into water and extracted with methylene chloride. The methylene chloride fraction is washed with dilute sodium hydroxide solution and the base is acidified with dilute HCl. The acidified is extracted with methylene chloride and the organic aqueous layer is dried over a layer of product.

išgarinamas ir gaunama 0,926 g balto kietoevaporate to give 0.926 g of white solid

BMR (CDC13, 8,02 (lH,dd) ,NMR (CDCl 3 , 8.02 (1H, dd),

270 MHz), 8,19(lH,d), δ : l,20(9H,s),270 MHz), 8.19 (1H, d), δ: 1.20 (9H, s),

9, 69(IH,s) .9, 69 (1H, s).

7,79(lH,d) ,7.79 (1H, d),

StadijaStage

2-Trifluormetil-4-(2' , 2'-dimetilpropionamido)-N,Ndimetilbenzamido gavimasPreparation of 2-Trifluoromethyl-4- (2 ', 2'-dimethylpropionamide) -N, N-dimethylbenzamide

0,64 g oksalilchlorido 7 ml sauso eterio tirpalas maišant sulašinamas į 0,926 g 2-trifluormetil-4-(2',2'dimetilpropionamido)-benzoinės rūgšties 40-yje ml sauso eterio kambario temperatūroje. Lašinimo metu pridedamas 1 lašas DMF. Po 2 vai. pridedama dar 0,257 g oksalilchlorido ir reakcijos mišinys papildomai maišomas 2 vai. Po to organinis tirpalas dekantuoj amas nuo nuosėdų, išgarinamas ir gaunama 1,136 g 2-trifluormetil-4-(2',2'-dimetilpropionamido)-benzoilchlorido skysčio, kuris toliau naudojamas be valymo.A solution of 0.64 g of oxalyl chloride in 7 ml of dry ether is added dropwise to 0.926 g of 2-trifluoromethyl-4- (2 ', 2'-dimethylpropionamide) -benzoic acid in 40 ml of dry ether at room temperature. Add 1 drop of DMF during the drip. After 2 or. another 0.257 g of oxalyl chloride is added and the reaction mixture is stirred for a further 2 hours. The organic solution is then decanted from the precipitate, evaporated to give 1.136 g of 2-trifluoromethyl-4- (2 ', 2'-dimethylpropionamide) -benzoyl chloride, which is used without further purification.

1,136 g chloranhidrido 10-yje ml sauso THF maišant per 30 min. sulašinama į 1,0 g 40% vandeninio dimetilamino tirpalą 15 ml THF 0-5°C temperatūroje. Reakcijos mišiniui leidžiama sušilti iki kambario temperatūros ir 2,5 dienos laikoma, po to išpilamas i vandenį ir ekstrahuojamas etilacetatu. Etilacetatinė frakcija praplaunamas vandeniniu natrio bikarbonato tirpalu, po to praskiesta HCl ir vandeniu. Organinis sluoksnis išdžiovinamas ir gaunama 0,576 g balto kieto produkto, lyd.t. 198,7-199, 6°C.1.136 g of chloro anhydride in 10 ml of dry THF with stirring for 30 min. is added dropwise to a solution of 1.0 g of 40% aqueous dimethylamine in 15 ml of THF at 0-5 ° C. The reaction mixture was allowed to warm to room temperature and kept for 2.5 days, then poured into water and extracted with ethyl acetate. The ethyl acetate fraction was washed with aqueous sodium bicarbonate solution, then diluted with HCl and water. The organic layer was dried to give 0.576 g of a white solid, m.p. 198.7-199.6 ° C.

BMR (CDC13, 270 MHz), δ : l,35(9H,s), 2,80(3H,s), 3,12 (3H,s), 7,22(lH,d), 7,72(lH,s), 7,75(lH,dd), 7,85 (lH,d).NMR (CDCl 3 , 270 MHz), δ: 1.35 (9H, s), 2.80 (3H, s), 3.12 (3H, s), 7.22 (1H, d), 7.72 (1H, s), 7.75 (1H, dd), 7.85 (1H, d).

PavyzdysAn example

2.3.5.6- Tetrafluor-4-(2',2'-dimetilpropionamido)-N,Ndimetilbenzamido gavimas (6 junginys II lentelėje)2.3.5.6- Preparation of tetrafluoro-4- (2 ', 2'-dimethylpropionamide) -N, N-dimethylbenzamide (compound 6 in Table II)

StadijaStage

2.3.5.6- Xetrafluor-4-(2',2'-dimetilpropionamido)benzoato gavimas2.3.5.6- Preparation of Xetrafluoro-4- (2 ', 2'-dimethylpropionamide) benzoate

1,887 g metil-2,3,5,6-tetrafluor-4-aminobenzoato 5iuose ml sauso THF sudedama į maišomą kambario temperatūroje 0,764 g (55% dispersijos alyvoje) natrio hidrido suspensiją 70 ml sauso THF. Pasibaigus dujų išsikyrimui, į šaldomą mišinį lėtai sulašinama 1,127 g 2,2-dimetilpropionilchlorido 5-iuose ml sauso THF. Mišinys 1 vai. maišomas 10°C temperatūroje ir išpilamas į vandenį, po to ekstrahuojamas etilacetatu. Etilacetatinė frakcija praplaunama praskiesta HCl ir natrio bikarbonato tirpalu, praskiestu džiovinama, produkto.1.887 g of methyl 2,3,5,6-tetrafluoro-4-aminobenzoate in 5 ml of dry THF are added to a stirred solution of 0.764 g (55% of an oil dispersion) sodium hydride in 70 ml of dry THF at room temperature. After evolution of gas, 1.127 g of 2,2-dimethylpropionyl chloride in 5 ml of dry THF is slowly added dropwise to the cooled mixture. Blend for 1 hour. stirred at 10 ° C and poured into water, followed by extraction with ethyl acetate. The ethyl acetate fraction was washed with dilute HCl and sodium bicarbonate solution diluted to dryness.

vandeniniu išgarinama ir gaunama 2,44 g balto kietoevaporated with water to give 2.44 g of white solid

BMR (CDC13, 270 MHz), δNMR (CDCl 3 , 270 MHz), δ

7, 05(IH,s) .7.05 (1H, s).

l,36(9H,s), 3,97(3H,s),1.36 (9H, s), 3.97 (3H, s),

StadijaStage

2,3,5,6-Tetrafluor-4-(2',2'-dimetilpropionamido)benzoinės rūgšties gavimasPreparation of 2,3,5,6-Tetrafluoro-4- (2 ', 2'-dimethylpropionamide) benzoic acid

1,83 g metil-2,3,5,6-tetrafluor-4-(2',2'-dimetilpropionamido) -benzoato maišoma per naktį su 0,669 g kalio hidroksido, ištirpinto minimaliame vandens kiekyje 60yje ml dimetoksietano (DMF) ir po to išpilama į vandenį. Mišinys ekstrahuojamas etilacetatu. Vandeninė fazė parūgštinama ir ekstrahuojama etilacetatu, o etilacetatinis ekstraktas džiovinamas, išgarinamas ir gaunama 1,538 g gelsvo kieto produkto.1.83 g of methyl 2,3,5,6-tetrafluoro-4- (2 ', 2'-dimethylpropionamide) benzoate are stirred overnight with 0.669 g of potassium hydroxide dissolved in a minimum of 60 ml of dimethoxyethane (DMF) and this is poured into water. The mixture was extracted with ethyl acetate. The aqueous phase is acidified and extracted with ethyl acetate, and the ethyl acetate extract is dried, evaporated to give 1.538 g of a yellow solid.

BMR (CDC13, 270 MHz), 6 : l,19(9H,s), 9,65(lH,s).NMR (CDCl 3 , 270 MHz), 6: 1.19 (9H, s), 9.65 (1H, s).

StadijaStage

2,3,5,6-Tetrafluor-4-(2',2'-dimetilpropionamido)-N,Ndimetilbenzamido gavimasPreparation of 2,3,5,6-Tetrafluoro-4- (2 ', 2'-dimethylpropionamide) -N, N-dimethylbenzamide

1,00 g oksalilchlorido 5 ml sauso eterio tirpalas maišant sulašinamas i, 1,47 g 2,3,5,6-tetrafluor-4(22'-dimetilpropionamido)-benzoinės rūgšties 35-iuose ml sauso eterio, i kurį pridėtas lašas DMF, 2 valandas maišoma kambario temperatūroje, po to tirpalas dekantuoj amas nuo netirpių junginių, išgarinamas ir gaunama 1,494 g chloranhidrido alyvos, kuri toliau naudojama be valymo.A solution of 1.00 g of oxalyl chloride in 5 ml of dry ether is added dropwise with stirring to 1.47 g of 2,3,5,6-tetrafluoro-4- (22'-dimethylpropionamide) benzoic acid in 35 ml of dry ether with a drop of DMF. After stirring for 2 hours at room temperature, the solution is decanted from the insoluble compounds, evaporated to give 1.494 g of chloro anhydride oil which is used without further purification.

1,494 g chloranhidrido 10-yje ml sauso THF lėtai, per 30 min., sulašinama į 1,363 g dimetilamino 10-yje ml THF 0-5°C temperatūroje. Reakcijos mišinys 1,5 vai. maišomas 10°C temperatūroje, po to išpilamas į vandenį ir ekstrahuojamas etilacetatu. Ekstraktas praplaunamas vandeniniu natrio bikarbonato tirpalu, po to praskiedžiamas HCl, džiovinamas, išgarinamas ir gaunamas miltelių pavidalo baltas kietas produktas (1,279 g), lyd.t. 187-189°C.1.494 g of chloro anhydride in 10 ml of dry THF are added slowly over 30 min to 1.363 g of dimethylamine in 10 ml of THF at 0-5 ° C. Reaction mixture for 1.5 hours. stirred at 10 ° C, then poured into water and extracted with ethyl acetate. The extract was washed with aqueous sodium bicarbonate solution, then diluted with HCl, dried, evaporated to give a white solid (1.279 g), m.p. 187-189 ° C.

BMR (CDCI3, 270 MHz), δ : l,35(9H,s), 2,97(3H,s),NMR (CDCl 3, 270 MHz), δ: 1.35 (9H, s), 2.97 (3H, s),

3, 17(3H,s), 7,82(IH,s) .3.17 (3H, s), 7.82 (1H, s).

PavyzdysAn example

2-Chlor-4-(2'-fluor-2'-metilpropionamido)-N,Ndimetibenzamido gavimas (38 junginys I lentelėje)Preparation of 2-Chloro-4- (2'-fluoro-2'-methylpropionamide) -N, N-dimethylbenzamide (Compound 38 in Table I)

0,60 g sidabro tetrafluorborato 5-iuose ml acetonitrito pridedama į 1,065 g 2-chlor-4-(2'-brom-2'-metilpropionamido)-N,N-dimetilbenzamido 150 ml acetonitrilo ir reakcijos mišinys 6,5 vai. maišomas azoto atmosferoje, saugant nuo šviesos. Į tirpalą pridedama etilacetato, filtruojama per ceolitą ir išgarinama. Liekana išvaloma didelės skiriamosios galios skysčio chromatografija (HLPC) —(eliuentas metilenchloridas/acetonitrilas (2:1) ir gaunama 0,319 g balto kristalinio produkto, lyd.t. 125-128°C.0.60 g of silver tetrafluoroborate in 5 ml of acetonitrile is added to 1.065 g of 2-chloro-4- (2'-bromo-2'-methylpropionamide) -N, N-dimethylbenzamide in 150 ml of acetonitrile and the reaction mixture is stirred for 6.5 hours. stirred under nitrogen atmosphere, protected from light. Ethyl acetate was added to the solution, filtered through zeolite and evaporated. The residue was purified by high-performance liquid chromatography (HLPC) (eluent: methylene chloride / acetonitrile (2: 1)) to give 0.319 g of a white crystalline product, mp 125-128 ° C.

BMR (CDC13, 270 MHz), δ : l,67(6H,d), 2,87(3H,s),NMR (CDCl 3 , 270 MHz), δ: 1.67 (6H, d), 2.87 (3H, s),

3,13(3H,s), 7,27(lH,d), 7,45(lH,dd), 7,80(lH,d),3.13 (3H, s), 7.27 (1H, d), 7.45 (1H, dd), 7.80 (1H, d),

8,18 (lH,d) .8.18 (1H, d).

PavyzdysAn example

2-Chlor-4-(3'-fluor-2' , 2'-dimetilpropionamido)-N,Ndimetilbenzamido gavimas (42 junginys I lentelėje)Preparation of 2-Chloro-4- (3'-fluoro-2 ', 2'-dimethylpropionamide) -N, N-dimethylbenzamide (Compound 42 in Table I)

StadijaStage

2-Chlor-4-(3'-acetoksi-2',2'-dimetilpropionamido)-N,Ndimetilbenzamido gavimasPreparation of 2-Chloro-4- (3'-acetoxy-2 ', 2'-dimethylpropionamide) -N, N-dimethylbenzamide

7,84 g 3-acetoksi-2,2-dimetilpropiochlorido pridedama į maišomą 0-5°C temperatūroje 5.88 g 4-amino-2-chlor-N,Ndimetilbenzamido ir 5,99 g trietilamino tirpalą 15-oje sauso metilenchlorido. Reakcijos mišinys 30 min. maišomas, praplaunamas praskiestu vandeniniu natrio bikarbonato tirpalu, praskiestu natrio hidroksidų, praskiesta HCl, po to vandeniu. Organinis sluoksnis džiovinamas, išgarinamas, o gautas kietas oranžinis junginys sutrinamas su heksanu, gaunant 9,08 g norimo produkto, lyd.t. 117-120°C.7.84 g of 3-acetoxy-2,2-dimethylpropiochloride are added to a stirred solution of 5.88 g of 4-amino-2-chloro-N, N-dimethylbenzamide and 5.99 g of triethylamine in 15 dry methylene chloride at 0-5 ° C. Reaction mixture for 30 min. stirred, washed with dilute aqueous sodium bicarbonate, diluted with sodium hydroxide, diluted with HCl, then with water. The organic layer was dried, evaporated and the resulting orange solid was triturated with hexane to give 9.08 g of the desired product, m.p. 117-120 ° C.

BMR (CDC13 270 MHz), δ : l,33(6H,s), 2,10(3H,s), 2,86 (3H,s), 3,13(3H,s), 4,20(2H,s), 7,ll(lH,d), 7,29 (lH,dd), 7,60(lH,d), 8,21(lH,s).NMR (CDCl 3 270 MHz), δ: 1.33 (6H, s), 2.10 (3H, s), 2.86 (3H, s), 3.13 (3H, s), 4.20 ( 2H, s), 7.11 (1H, d), 7.29 (1H, dd), 7.60 (1H, d), 8.21 (1H, s).

IR (nujolas) : 1740, 1680, 1630 cm1.IR (nujol): 1740, 1680, 1630 cm @ -1 .

StadijaStage

2-Chlor-4-(3'-hidroksi-2',2'-dimetilpropionamido)-N,Ndimetilbenzamido gavimasPreparation of 2-Chloro-4- (3'-hydroxy-2 ', 2'-dimethylpropionamide) -N, N-dimethylbenzamide

8,14 g 2-chlor-4-(3'-acetoksi-2',2'-dimetilpropionamido) -N, N-dimetilbenzamido 2 vai. maišoma kambario temperatūroje 100-e ml etanolio, turinčio 2,68 g kalio hidroksido. Metanolis išgarinamas, o nuosėdos ekstrahuojamos etilacetatu. Etilacetatas džiovinamas, išgarinamas ir gaunama 5,03 g produkto, lyd.t. 137139°C.8.14 g of 2-chloro-4- (3'-acetoxy-2 ', 2'-dimethylpropionamide) -N, N-dimethylbenzamide 2 or 2. is stirred at room temperature in 100 ml of ethanol containing 2.68 g of potassium hydroxide. The methanol was evaporated and the residue was extracted with ethyl acetate. The ethyl acetate is dried, evaporated to give 5.03 g of product, m.p. 137139 ° C.

BMR (CDCI3, 270 MHz), δ : l,17(6H,s), 2,89(3H,s), 3,15 (3H,s), 3,56(3H,d), 5,12(lH,t), 7,17(lH,d), 7,30 (lH,dd), 7,69(lH,d), 9,49(lH,s).NMR (CDCl 3, 270 MHz), δ: 17 (6H, s), 2.89 (3H, s), 3.15 (3H, s), 3.56 (3H, d), 5.12 ( 1H, t), 7.17 (1H, d), 7.30 (1H, dd), 7.69 (1H, d), 9.49 (1H, s).

StadijaStage

2-Chlor-4-(3’-fluor-2',2'-dimetilpropionamido)-N,Ndimetilbenzamido gavimasPreparation of 2-Chloro-4- (3'-fluoro-2 ', 2'-dimethylpropionamide) -N, N-dimethylbenzamide

1,008 g 2-chlor-4-(3'-hidroksi-2',2'-dimetilpropionamido) -N,N-dimetilbenzamido 40-yje ml sauso metilenchlorido per 3 vai. sulašinama į 0,68 g dietilamino sieros trifluorido tirpalą (DAST) 20 ml sauso metilenchlorido -70°C temperatūroje. Po 0,5 vai. pridedama papildomai 0,128 g DAST, tirpalas 0,5 vai. maišomas -70°C temperatūroje, po to paliekamas per naktį sušilti iki kambario temperatūros. Reakcijos mišinys praplaunamas vandeniu, džiovinamas, išgarinamas ir gaunamos putos. Jos sutrinamos su heksanu ir gaunama1.008 g of 2-chloro-4- (3'-hydroxy-2 ', 2'-dimethylpropionamide) -N, N-dimethylbenzamide in 40 ml of dry methylene chloride over 3 hours. is added dropwise to 0.68 g of diethylamine sulfur trifluoride solution (DAST) in 20 ml of dry methylene chloride at -70 ° C. After 0.5 or. addition of 0.128 g DAST, 0.5 h solution. stirred at -70 ° C, then allowed to warm to room temperature overnight. The reaction mixture is washed with water, dried, evaporated to give a foam. They are triturated with hexane and obtained

0,269 g šviesiai oranžinių miltelių, lyd.t. 152-154°C.0.269 g light orange powder, m.p. 152-154 ° C.

BMR (CDC13, 270 MHz), δ : l,32(6H,d), 2,86(3H,s),NMR (CDCl 3 , 270 MHz), δ: 1.32 (6H, d), 2.86 (3H, s),

3,12(3H,s), 4,48(2H,d), 7,23(lH,d), 7,39(lH,dd),3.12 (3H, s), 4.48 (2H, d), 7.23 (1H, d), 7.39 (1H, dd),

7,75 (lH,d) , 7,77 (1H, s) .7.75 (1H, d), 7.77 (1H, s).

PavyzdysAn example

2-Chlor-4-(3'-metoksi-2',2'-dimetilpropionamido)-N,Ndimetilbenzamido gavimas (40 junginys I lentelėje)Preparation of 2-Chloro-4- (3'-methoxy-2 ', 2'-dimethylpropionamide) -N, N-dimethylbenzamide (Compound 40 in Table I)

2,608 g bario oksido ir 0,54 g hidroksido pridedama i 0,510 g 2-chlor-4-(3'-hidroksi-2’,2'-dimetilpropionamido) -N, N-dimetilbenzamido tirpalą 20 ml DMF 0°C temperatūroje 15 min. maišoma 0°C temperatūroje, po to įlašinama 3,64 g metiljodido. Per 2 vai. leidžiama mišiniui sušilti iki kambario temperatūros, pridedama metilenchlorido, o po to mišinys filtruojamas per ceolitą. Organinė frakcija džiovinama, išgarinama ir gaunamas nepastovus skystis, kuris išvalomas HPLC (eliuentas: etilacetats) ir gaunama 0,101 g kieto produkto, lyd.t. 101-103QC.2.608 g of barium oxide and 0.54 g of hydroxide are added to a solution of 0.510 g of 2-chloro-4- (3'-hydroxy-2 ', 2'-dimethylpropionamide) -N, N-dimethylbenzamide in 20 ml of DMF at 0 ° C for 15 min. . After stirring at 0 ° C, 3.64 g of methyl iodide are added dropwise. Within 2 or. the mixture was allowed to warm to room temperature, methylene chloride was added and the mixture was then filtered through zeolite. The organic fraction is dried, evaporated to give a volatile liquid which is purified by HPLC (eluent: ethyl acetate) to give 0.101 g of a solid, m.p. 101-103 Q C.

BMR (CDCI3, 270 MHz), δ : l,24(6H,s), 2,86(3H,s), 3,12 (3H,s), 3,43(2H,s), 3,51(3H,s), 7,21(lH,d), 7,39 (lH,dd), 7,75(lH,d), 9,05(lH,s).NMR (CDCl 3, 270 MHz), δ: 1.24 (6H, s), 2.86 (3H, s), 3.12 (3H, s), 3.43 (2H, s), 3.51 ( 3H, s), 7.21 (1H, d), 7.39 (1H, dd), 7.75 (1H, d), 9.05 (1H, s).

PavyzdysAn example

2-Chlor-4-(2',2'-dimetil-tiopropionamido)-N,N-dimetiltiobenzamido ir 2-chlor-4-(2',2'-dimetilpropionamido)N, N-dimetil-tiobenzamido gavimas ( 3 ir 1 junginiai atitinkamai III lentelėje)Preparation of 2-chloro-4- (2 ', 2'-dimethylthiopropionamide) -N, N-dimethylthiobenzamide and 2-chloro-4- (2', 2'-dimethylpropionamide) N, N-dimethylthiobenzamide (3 and 1 compounds in Table III, respectively)

1,00 g 2-chlor-4-(2',2'-dimetilpropionamido)-N,N-dimetilbenzamido suspenduojama 10 ml sauso toluolo ir nedidelėmis porcijomis per 5 min. pridedama 0,75 g Lavesono reagento kambario temperatūroje. Suspensija 1 vai. virinama su grįžtamuoju šaldytuvu, gaunant skaidrų skystą, toluenas išgarinamas ir gaunama klampi derva, kuri chromatografuojama per silikagelą (eliuentas:metilenchloridas). Gaunami du produktai:1.00 g of 2-chloro-4- (2 ', 2'-dimethylpropionamide) -N, N-dimethylbenzamide are suspended in 10 ml of dry toluene and in small portions over 5 min. 0.75 g of Laveson's reagent was added at room temperature. Suspension 1 or. refluxing to give a clear liquid, evaporating the toluene to give a viscous gum which is chromatographed on silica gel (eluent: methylene chloride). Two products are obtained:

1. 2- (chlor-4-(2',2'-dimetilpropionamido)-N,N-dimetiltiobenzamidas (0,104 g), lyd.t. 154-156°C.1. 2- (Chloro-4- (2 ', 2'-dimethylpropionamide) -N, N-dimethylthiobenzamide (0.104 g), mp 154-156 ° C.

BMR (CDC13, 270 MHz), δ : l,47(9H,s), 3,14(3H,s),NMR (CDCl 3 , 270 MHz), δ: 1.47 (9H, s), 3.14 (3H, s),

3,60(3H,s), 7,29(lH,d), 7,52(lH,dd), 7,82(lH,s),3.60 (3H, s), 7.29 (1H, d), 7.52 (1H, dd), 7.82 (1H, s),

8,85(IH,ps).8.85 (1H, ps).

2. 2-Chlor-4-(2',2'-dimetilpropionamido)-N,N-dimetiltiobenzamidas (0,475 g), lyd.t. 164-167°C.2. 2-Chloro-4- (2 ', 2'-dimethylpropionamide) -N, N-dimethylthiobenzamide (0.475 g), m.p. 164-167 ° C.

BMR (CDC13, 270 MHz), δ : l,31(9H,s), 3,ll(3H,s), 3,58(3H,s), 7,25(lH,d), 7,33(lH,dd), 7,38(lH,ps), 7,74 (lH,s) .NMR (CDCl 3 , 270 MHz), δ: 1.31 (9H, s), 3.11 (3H, s), 3.58 (3H, s), 7.25 (1H, d), 7.33 (1H, dd), 7.38 (1H, ps), 7.74 (1H, s).

PavyzdysAn example

2- Chlor-4- (2 ', 2 ' -dimetil-tiopropionamido) -N,lydime t i lben z amido (2 junginys III lentelėje) gavimasPreparation of 2-Chloro-4- (2 ', 2' -dimethyl-thiopropionamide) -N, m.p.

StadijaStage

3- Chlor-4-N,N-dimetilkarbomoil-fenil-izotiocianato gavimasPreparation of 3-Chloro-4-N, N-dimethylcarbomoyl-phenyl-isothiocyanate

1,15 g tiofosgeno per 3 min. sulašinama ą 1,68 g natrio bikarbonato suspenduojamo vandenyje ir maišomo kambario temperatūroje. Po to per 20 min. porcijomis pridedama 1,00 g 4-amino-2-chlor-N,N-dimetilbenzamido, palaikant 20-25°C temperatūrą. Po 15 min. ruda suspensija ekstrahuojama metilenchloridu, o organinis sluoksnis džiovinamas ir išgarinamas, gaunama 1,18 g gelsvaioranžinio kieto produkto, toliau naudojamo be valymo.1.15 g of thiophosgene in 3 min. drip 1,68 g of sodium bicarbonate suspended in water and stirred at room temperature. After that, within 20 minutes. 1.00 g of 4-amino-2-chloro-N, N-dimethylbenzamide were added portionwise, maintaining the temperature at 20-25 ° C. After 15 minutes the brown suspension is extracted with methylene chloride and the organic layer is dried and evaporated to give 1.18 g of a yellow-orange solid which is used without further purification.

BMR (CDC13, 270 MHz), δ : 2,86(3H,s), 3,13(3H,s), 7,17(lH,dd), 7,26(lH,s), 7,28(lH,d).NMR (CDCl 3 , 270 MHz), δ: 2.86 (3H, s), 3.13 (3H, s), 7.17 (1H, dd), 7.26 (1H, s), 7.28 (1H, d).

IR (nujolas) : 2140-2080, 1630 cm1.IR (nujol): 2140-2080, 1630 cm @ -1 .

StadijaStage

2-Chlor-4-(2',2'-dimetil-tiopropionamido)-N,Ndimetilbenzamido gavimasPreparation of 2-Chloro-4- (2 ', 2'-dimethyl-thiopropionamide) -N, N-dimethylbenzamide

3,2 ml 1,7M tret-butilličio tirpalo pentane per 20 min. pridedama į maišomą 1,17 g 3-chlor-4-N,N-dimetilkarbamoilfenilizocianato tirpalą THF azoto atmosferoje, -70°C temperatūroje. 20 min. maišoma toje pačioje temperatūroje, atsargiai pridedama vandens, po to koncentruotos HCl. Mišinys ekstrahuojamas metilenchloridu, džiovinamas, ekstrahuojamas ir gaunama 1,23 g lipnaus rudo kieto produkto. Jis išvalomas HPLC (eliuentas:etilacetatas) ir dervos. Ji sutrinama su gaunamas geltonas kietas (suskylant).3.2 ml of a 1.7M solution of tert-butyl lithium in pentane over 20 min. is added to a stirred solution of 1.17 g of 3-chloro-4-N, N-dimethylcarbamoylphenyl isocyanate in THF under nitrogen atmosphere at -70 ° C. 20 mins stirred at the same temperature, carefully added water, then concentrated HCl. The mixture was extracted with methylene chloride, dried, and extracted with 1.23 g of a sticky brown solid. It is purified by HPLC (eluent: ethyl acetate) and resins. It is rubbed with the resulting yellow solid (by decomposition).

BMR (CDC13, 270 MHz), δNMR (CDCl 3 , 270 MHz), δ

3,14(3H,s), 7,25(lH,d),3.14 (3H, s), 7.25 (1H, d),

8,82 (lH,ps) .8.82 (1H, ps).

PavyzdysAn example

2-Chlor-4-(2',2'-dimetilpent dimetilbenzamido (66 jungini gaunama 0,099 g geltonos eterio/toluolo mišiniu ir produktas, lyd.t. 120°C : l,66(9H,s), 2,88(3H,s),2-Chloro-4- (2 ', 2'-dimethylpentylbenzamide (Compound 66) is obtained in a mixture of 0.099 g of a yellow ether / toluene mixture and the product, m.p. 120 ° C: 1.66 (9H, s), 2.88 3H, s),

7,45(lH,dd), 7,64(lH,d), ’ -inamido) -N,NI lentelėje) gavimas7.45 (1H, dd), 7.64 (1H, d), '-inamido) -N, NI in Table)

Etil-2,2-dimetilpent-4-inoato gavimasPreparation of ethyl 2,2-dimethylpent-4-ynoate

13,7 ml ličio diizopropilamido (1,5M mono-THF-komplekso tirpalo cikloheksane) per 20 min. sulašinama i, maišomą13.7 mL of lithium diisopropylamide (1.5M solution of mono-THF complex in cyclohexane) over 20 min. drip, stirring

2.38 g etilizobutirato tirpalą 10 ml sauso THF azoto atmosferoje, palaikant temperatūrą žemiau -60°C. Po 1 vai. sulašinama 2,45 g propargilbromido 5-iuose ml THF, palaikant temperatūrą žemiau -60°C. Reakcijos mišiniui leidžiama sušilti iki kambario temperatūros per 2 vai., po to jis išpilamas į vandenį ir ekstrahuojamas etilacetatu. Etilacetatinė frakcija džiovinama, išgarinama ir gaunamas rudai-oranžinis skystis, kuris perdistiliuojamas (Kugelrohr, 115°C/60 mm) ir gaunamaA solution of 2.38 g of ethyl isobutyrate in 10 ml of dry THF under nitrogen at a temperature below -60 ° C. After 1 or. 2.45 g of propargyl bromide in 5 ml of THF are added dropwise at a temperature below -60 ° C. The reaction mixture was allowed to warm to room temperature over 2 hours, after which it was poured into water and extracted with ethyl acetate. The ethyl acetate fraction is dried, evaporated to give a brown-orange liquid which is redistilled (Kugelrohr, 115 ° C / 60 mm) to give

1.39 g produkto.1.39 g of product.

BMR (CDC13, 270 MHz), δ : l,19(3H,t), l,21(6H,s), l,93(lH,t), 2,38(2H,d), 4,08(2H,kv).NMR (CDCl 3 , 270 MHz), δ: 1.19 (3H, t), 1.21 (6H, s), 1.93 (1H, t), 2.38 (2H, d), 4.08 (2H, s).

StadijaStage

2,2-Dimetilpent-4-ino rūgšties gavimasPreparation of 2,2-dimethylpent-4-ynoic acid

1,39 g etil-2,2-dimetilpent-4-inoato 7,5 vai. maišoma su 1,07 g kalio hidroksido 20-yje ml metanolio 40°C temperatūroje, o po to mišinys laikomas per naktį. Mišinys išpilamas į vandenį ir praplaunamas etilacetatu. Vandeninis sluoksnis parūgštinamas ir ekstrahuojamas etilacetatu. Šis sluoksnis po to džiovinamas, išgarinamas ir gaunama 1,05 g skystos rūgšties.1.39 g of ethyl 2,2-dimethylpent-4-ynoate 7.5 or. mixed with 1.07 g of potassium hydroxide in 20 ml of methanol at 40 ° C and the mixture is then kept overnight. The mixture is poured into water and washed with ethyl acetate. The aqueous layer was acidified and extracted with ethyl acetate. This layer was then dried, evaporated to give 1.05 g of liquid acid.

BMR (CDC13, 270 MHz), δ : l,32(6H,s), 2,04(lH,t),NMR (CDCl 3 , 270 MHz), δ: 1.32 (6H, s), 2.04 (1H, t),

2,47(2H,d).2.47 (2 H, d).

IR (skysta plėvelė) : 3300, 3000-2500, 1720 cm'1.IR (liquid film): 3300, 3000-2500, 1720 cm &lt; -1 &gt;.

StadijaStage

2-Chlor-4-(2',2'-dimetilpent-4-inamido)-N,Ndimetilbenzamido gavimas ml 2,2-dimetilpent-4-ino rūgšties maišoma kambario temperatūroje 15-oje ml sauso eterio ir maišant sulašinama 1,53 g oksalilchlorido 5-iuose ml sauso eterio. Po to mišinys 0,5 vai. maišomas.Preparation of 2-Chloro-4- (2 ', 2'-dimethylpent-4-ylamide) -N, N-dimethylbenzamide In ml of 2,2-dimethylpent-4-ynoic acid was stirred at room temperature in 15 ml of dry ether and dropwise 1.53 g of oxalyl chloride in 5 ml of dry ether. The mixture was then stirred for 0.5 h. stirring.

Mišinys dekantuojamas, eteris išgarinamas ir gaunama 0,417 g_ chloranhidrido, balzgano skysčio, toliau naudojamo be valymo.The mixture was decanted, the ether evaporated to give 0.417 g of chloro anhydride, a whitish liquid further used without purification.

maišomą 0,524 g 4-amino-2-chlor-N,N-dimetilbenzamido ir 0,534 g trietilamino tirpalą 0-5°C temperatūroje pridedama 0,417 g 2,2-dimetilpent-4-ino rūgšties chloranhidrido. Reakcijos praplaunamas praskiesta bikarbonato tirpalu ir mišinys 1,5 vai. maišomas, HCl, vandeniniu natrio vandeniu. Metilenchlorido tirpalas džiovinamas, išgarinamas ir gaunamos putos, kurios kristalizuojamos ir gaunama 0,606 g šviesiai oranžinio kieto produkto, lyd.t. 154-155°C.To a stirred solution of 0.524 g of 4-amino-2-chloro-N, N-dimethylbenzamide and 0.534 g of triethylamine at 0-5 ° C was added 0.417 g of 2,2-dimethylpent-4-ynoic acid chloro anhydride. The reaction was washed with dilute bicarbonate solution and the mixture for 1.5 hours. stirred with HCl, aqueous sodium water. The methylene chloride solution is dried, evaporated to give a foam which crystallizes to give 0.606 g of a light orange solid, m.p. 154-155 ° C.

BMR (CDC13, 2,52 (2H,d) ,NMR (CDCl 3 , 2.52 (2H, d),

270 MHz), δ 2, 87(3H,s),270 MHz), δ 2, 87 (3H, s),

1,40(6H,s), 3, 13(3H,s),1.40 (6H, s), 3.13 (3H, s),

2,17 (lH,t) , 7,05 (lH,d) ,2.17 (1H, t), 7.05 (1H, d),

7,33(lH,dd), 7,64(lH,d) .7.33 (1H, dd), 7.64 (1H, d).

Žemiau pateiktos kompozicijos, į kurias Įeina šio išradimo junginiai, tinka agrocheminiams ir žemės ūkio tikslams, procentai - tai svorio procentai.The percentages of the compositions below which include the compounds of this invention are suitable for agrochemical and agricultural purposes, and are by weight.

PavyzdysAn example

Emulguojamas koncentratas, gaunamas sumaišant ir permaišant komponentus iki visiško jų ištirpimo.An emulsifiable concentrate obtained by mixing and mixing the components until they are completely dissolved.

Junginys I lentelėje 10%Compound in Table I 10%

Benzilo alkoholis 30%Benzyl alcohol 30%

Kalcio dodecilbenzolsulfonatasCalcium dodecylbenzene sulphonate

5%5%

Nonilfenoletoksilatas (13 molių etilenoksido) 10%Nonylphenol ethoxylate (13 moles ethylene oxide) 10%

Alkilenbenzenas 45%Alkylbenzene 45%

PavyzdysAn example

Aktyvus komponentas ištirpinamas metilenchloride ir tuo 5 tirpalu apipurškiamos atapulgitino molio granulės. Po to tirpikliui leidžiama išgaruoti ir gaunama granulių kompozicija.The active component is dissolved in methylene chloride and this solution is sprayed with granules of atapulgitin clay. The solvent is then allowed to evaporate to give a granular composition.

Junginys I lentelėje 5%Compound in Table I 5%

Atapulgitinės granulės 95%Atapulgitic granules 95%

15 Pavyzdys 15 Example Kompozicija, tinkama sėklų apdirbimui, ir sumaišant tris komponentus. A composition suitable for seed treatment and mixing three components. gaunama sumalant obtained by grinding 3 Junginys I lentelėje 3 Compound in Table I 50% 50% Neorganinis aliejus Inorganic oil 2% 2% Kaolinas Kaolin 48% 48%

PavyzdysAn example

Dulkės, gaunamos sutrinant komponentą su talku. Dust obtained by crushing component with talc. ir and sumaišant by mixing aktyvų active 4 Junginys I lentelėje 4 Compound in Table I 5% 5%

TalkasTalk

95%95%

PavyzdysAn example

Suspensinis mišinys gaunamas, sumaišant komponentus rutuliniame malūne ir gaunant sumalto mišinio suspensiją vandenyje.The slurry mixture is obtained by mixing the components in a ball mill and obtaining a slurry slurry in water.

Junginys I lentelėje 40%Compound in Table I 40%

Natrio lignisulfonatas 10%Sodium lignisulfonate 10%

Bentonito molis 1%Bentonite clay 1%

Vanduo 49%Water 49%

Šį sąstatą galima išpurkšti praskiedus vandeniu arba tiesiai apdoroti juo sėklas.This assembly can be sprayed with dilution with water or directly treated with seeds.

PavyzdysAn example

Drėkstantys milteliai gaunami sumalant komponentus.The wetting powder is obtained by grinding the components.

Junginys I lentelėjeCompound in Table I

Natrio laurilsulfatasSodium laurilsulfate

Natrio ligninsulfonatasLignin sulphonate sodium

Silicio dioksidasSilica

Kaolinas rūpestingai sumaišant irKaolin by careful mixing and

25%25%

2%2%

5%5%

25%25%

43%43%

PavyzdysAn example

Junginiai tiriami panaudojimui prieš augalų lapų grybelinius susirgimus. Taikoma tokia metodika.The compounds are tested for use against fungal diseases of plant leaves. The following methodology is used.

Augalai auginami 4 cm diametro puodeliuose John InnesThe plants are grown in 4 cm diameter pots by John Innes

Potting Compost (Nr. 1 arba 2) komposte. Tiriami junginiai sumalami rutuliniame malūne su vandeniniuPotting Compost (No. 1 or 2) in compost. Test compounds are ground in a ball mill with water

Dispersol T arba naudojami acetono arba acetono/ etanolio tirpale, kuris praskiedžiamas koncentracijos prieš pat naudojimą, susirgimams, mišiniu apipurškiami lapai iki norimos Esant lapų komponento) (lOOd/mln aktyvaus ir augalų šaknys dirvoje.Dispersol T or used in case of illness in acetone or acetone / ethanol solution, which is diluted to a concentration just before use, spray the leaves to the desired presence of leaf component) (100d / million active and plant roots in soil.

Apipurškiama taip, kad maksimaliai išsilaikytų, o šaknys apdorojamos tol, kol aktyvaus komponento kompozicija sausoje dirvoje siekia 40 d/mln. Apipurškiant varpinius augalus, pridedama Tween 20 iki 0,05% koncentracijos.Spray to maximize retention and root treatment until the active ingredient has a dry soil composition of 40 d / million. Tween 20 is added at a concentration of 0.05% when spraying bell plants.

Dažniausiai tiriamais junginiais apdorojama dirva (šaknys) ir lapai (apipurškiant) 1-2 dienas iki augalų užkrėtimo ligos sukėlėju. Išimtimi buvo bandymas su Erysiphe graminis, kai augalai buvo užkrėsti 24 vai. prieš apdorojimą. Augalai užkrečiami, apipurškiant tiriamų augalų lapus sporų suspensijomis. Užkrėsti augalai laikomi tinkamoje infekcijos paplitimui aplinkoje ir po to inkubuojami tol, kol susirgimą galima Įvertinti. Priklausomai nuo aplinkos ir susirgimo, tarp užkrėtimo ir susirgimo Įvertinimo praeina 4-14 dienų.The most commonly used compounds are applied to the soil (roots) and leaves (spraying) 1-2 days before the infestation of the plants with the pathogen. An exception was the Erysiphe graminis test when the plants were infected for 24 hours. before processing. The plants are infected by spraying the leaves of the test plants with spore suspensions. The infected plants are kept in a suitable environment for the spread of infection and then incubated until the disease can be assessed. Depending on the environment and the disease, it takes 4-14 days between the infection and the assessment of the disease.

Susirgimo slopinimas Įvertinamas šiais rezultatais:Inhibition of illness is evaluated by the following results:

= nėra susirgimo = pėdsakai-5% nuo susirgusių neapdorotų augalų 2 = 6-25% nuo susirgusių neapdorotų augalų 1 = 26-59% nuo susirgusių neapdorotų augalų 0 = 60-100% nuo susirgusių neapdorotų augalų= no disease = traces -5% of untreated plants 2 = 6-25% of untreated plants 1 = 26-59% of untreated plants 0 = 60-100% of untreated plants

Rezultatai pateikiami IV, V ir VI lentelėse.The results are shown in Tables IV, V and VI.

IV LENTELETO TABLE IV

Phytoph thor a Infestans (Pomidorai) Phytoph thor a Infestans (Tomatoes) Plasmopara Viticola (Vynmedžiai) Plasmopara Viticola (Vines) Ν’Ν’ΟΝ’Ν’Ν’ΓΟΓΩΝ’Ν’Ν’Ν’Ν* ΝΝΝΝΟΝΝΝΝΓΟΓΩΝΓΟΓΩΝΝΝΝΝΝ * Cercospora Arachidicola (Žemės riešutai) Cercospora Arachidicola (Peanuts) OOO 1 CNOOTr-JOOO 1 OOO 1 CNOOTr-JOOO 1 Venturia Inaecjualis (Obelys) Venturia Inaecjualis (Apple tree) o r-ι o m’ v 'T i v o o co o i o r-ι o m 'v' T i v o o co o i Erysiphe Graminis (Miežiai) Erysiphe Grammatical (Barley) ooo<-HOf\j«rooooo.-i ooo <-HOf \ j «rooooo.-i Puccinia Recondita (Kviečiai) Puccinia Recondita (Wheat) ojcsioonN’cncncsiooooN’ ojcsioonN'cncncsiooooN ' Junginio Nr. iš I lentelės Compound No. from Table I

IV LENTELE (tęsinys)TABLE IV (cont'd)

Phytophthor a Infestans (Pomidorai) Phytophthor a Infestans (Tomatoes) Plasmopara Viticola (Vynmedžiai) Plasmopara Viticola (Vines) Cercospora Arachidicola (Žemės riešutai) Cercospora Arachidicola (Peanuts) OrdOCsJOOOOOO 1 o OrdOCsJOOOOOO 1 o Venturia Inaequalis (Obelys) Venturia Inaequalis (Apple tree) l lo^roooojoom’T l lo ^ roooojoom'T Erysiphe Graminis (Miežiai) Erysiphe Grammatical (Barley) OOOOC-JCNOOOOr-li-l OOOOC-JCNOOOOr-li-l Puccinia Recondita (Kviečiai) Puccinia Recondita (Wheat) ^rroooooooooj^ro ^ rroooooooooj ^ ro Junginio Nr. iš I lentelės Compound No. from Table I ^r’LO'Zir^oocrio,—ic\ic)vrLO >-1 <-l <-1 r—1 t—1 >-l 04 <M CM <M <N Csl ^ r'LO'Zir ^ oocrio, —ic \ ic) vrLO> -1 <-l <-1 r — 1 t — 1> -l 04 <M CM <M <N Csl

IV LENTELE (tęsinys)TABLE IV (cont'd)

Phytophthor a Infestans (Pomidorai) Phytophthor a Infestans (Tomatoes) Plasmopara Viticola (Vynmedžiai) Plasmopara Viticola (Vines) Cercospora Arachidicola (Žemės riešutai) Cercospora Arachidicola (Peanuts) mcMfUocMooomcooo i mcMfUocMooomcooo i Venturia Inaegualis (Obelys) Venturia Inaegualis (Apple tree) ooo'roocN’TO^J'o^ro ooo'roocN'TO ^ J'o ^ ro Erysiphe Graminis (Miežiai) Erysiphe Grammatical (Barley) OOOOOOOt—IOOCOOO OOOOOOOt — IOOCOOO Puccinia Recondita (Kviečiai) Puccinia Recondita (Wheat) OOOCOCNOr-ICMOOOOO OOOCOCNOr-ICMOOOOO Junginio Nr. iš I lentelės Compound No. from Table I kur^aacnor-iojco'rLOkDr'OO cMCMojcMforocoromroromm where ^ aacnor-iojco'rLOkDr'OO cMCMojcMforocoromroromm

IV LENTELE (tęsinys)TABLE IV (cont'd)

Phytophthor a Infestans (Pomidorai) Phytophthor a Infestans (Tomatoes) co ν’ co co co ν 'co co Plasmopara Viticola (Vynmedžiai) Plasmopara Viticola (Vines) co v co co co v co co Cercospora Arachidicola (Žemės riešutai) Cercospora Arachidicola (Peanuts) 1 1 o CO 1 1 o CO Venturia Inaequalis (Obelys) Venturia Inaequalis (Apple tree) CM o o 1 CM o o 1 Erysiphe Graminis (Miežiai) Erysiphe Grammatical (Barley) O O O CM O O O CM Puccinia Recondita (Kviečiai) Puccinia Recondita (Wheat) o o o m o o o m Junginio Nr. iš I lentelės Compound No. from Table I O <0 C- CO V kO kO kO O <0 C-CO V KO KO KO

V LENTELETABLE V

Phytophthora Infestans (Pomidorai) Phytophthora Infestans (Tomatoes) v v m 'r v o m v v m 'r v o m Plasmopara Viticola (Vynmedžiai) Plasmopara Viticola (Vines) o i m o i m Cercospora Arachidicola (Žemės riešutai) Cercospora Arachidicola (Peanuts) O O O O 1 CM 1 O O O O 1 CM 1 Venturia Inaequalis (Obelys) Venturia Inaequalis (Apple tree) o o o o o o o o o o o o o o o Erysiphe Graminis (Miežiai) Erysiphe Grammatical (Barley) O <-H O O 1 o o O <-H O O 1 o o Puccinia Recondita (Kviečiai) Puccinia Recondita (Wheat) o o o o o o o o o o o o o o o Junginio Nr. iš II lentelės Compound No. from Table II 1—1 CM m LO LO r— 1—1 CM m LO LO r—

VI LENTELETO TABLE VI

Phytophthora Infestans (Pomidorai) Phytophthora Infestans (Tomatoes) o o o o Plasmopara Viticola (Vynmedžiai) Plasmopara Viticola (Vines) Cercospora Arąchidicola (Žemės riešutai) Cercospora Arąchidicola (Peanuts) 1 1 1 1 Venturia Inaequalis (Obelys) Venturia Inaequalis (Apple tree) 1 1 1 1 Erysiphe Graminis (Miežiai) Erysiphe Grammatical (Barley) O (N O (N Puccinia Recondita (Kviečiai) Puccinia Recondita (Wheat) CN CN CN CN Junginio Nr. iš II lentelės Compound No. from Table II τ-l CO τ-l CO

Claims (1)

IŠRADIMO APIBRĖŽTISDEFINITION OF INVENTION 1. Junginio, kurio formulė (I) gavimo būdas kurioje A ir B nepriklausomai yra H, fluoras, chloras, bromas, Cx_4 alkilas, Cx_4 alkoksilas arba halogen (Cx_4) alkilas, su sąlyga, kad abu nėra H; D ir E nepriklausomai yra H arba fluoras; R1 yra H, Cr_4 alkilas arba Cx_4 alkoksilas; R yra Cw alkilas, Cx.4 alkoksilas arba pasirinktinai pakeistas fenilas, arba R1 ir R2 kartu su azoto atomu, prie kurio jie prijungti, sudaro morfolino, piperidino, pirolidino arba azetidino žiedą, pasirinktinai pakeistą C1_4alkilu; R3 yra H; o R4 yra trichlormetilas, C2_8 alkilas (pasirinktinai pakeistas halogenu, Cx_8 alkoksilu arba R'S(O)n grupe, kur R1 yra Cx,4 alkilas, C2.4 alkenilas arba C2_4alkinilas, o n yra 0, 1 arba 2) , ciklopropilas (pasirinktinai pakeistas halogenu arba Cx_4 alkilu) , C2.8 alkenilas, C2_8 alkoksilas, mono- arba di(Cx.4) alkilamino arba R' ΌΝ = C(CN) grupė, kur R'1 yra Cx.4 alkilas arba R3 ir R4 kartu su C (O) N grupe, prie kurios jie prijungti, sudaro azetidin-2-ono žiedą, pasirinktinai pakeistą halogenu arba alkilu, o X ir Y yra nepriklausomi deguonis arba siera, besiskiriantis tuo, kad:First a compound of formula (I) thereof, wherein A and B are independently H, fluoro, chloro, bromo, C x _ 4 alkyl, C x _ 4 alkoxy or halo (C x _ 4) alkyl, with the proviso that both are not H; D and E are independently H or fluoro; R 1 is H, C 1-4 alkyl or Cx-4 alkoxy; R is C 1 -C 4 alkyl, C 4 -C 4 alkoxyl, or optionally substituted phenyl, or R 1 and R 2 together with the nitrogen atom to which they are attached form a morpholine, piperidine, pyrrolidine or azetidine ring optionally substituted with C 1-4 alkyl; R 3 is H; and R 4 is trichloromethyl, C2_8 alkyl (optionally substituted with halogen, Cx_8 alkoxy or R'S (O) n group, wherein R 1 is Cl, 4 alkyl, C second 4 alkenyl or C 2 _ 4 alkinyl, on is 0, 1, or 2), cyclopropyl (optionally substituted with halo or C x 4 alkyl), C 2 . 8 alkenyl, C 2 _ 8 alkoxy, mono- or di (C x. 4) -alkylamino, or R 'ΌΝ = C (CN) group, wherein R' 1 is C x. 4 alkyl or R 3 and R 4 taken together with the C (O) N group to which they are attached form an azetidin-2-one ring optionally substituted with halogen or alkyl, and X and Y are independent oxygen or sulfur, wherein : a) (IX) formulės junginia) A compound of formula (IX) Cl // (IX), kurioje A, B, D, E ir R'' yra pažymėti aukščiau, veikia aminu R1R2NH, kur R1 ir R2 yra pažymėti aukščiau, atitinkamame organiniame tirpiklyje, dalyvaujant šarmui arba R1R2NH amino pertekliui ir, kai R5 ir R4 su grupe C(O)N sudaro žiedą, kurio formulė:Cl // (IX) wherein A, B, D, E, and R '' are as defined above, is reacted with the amine R 1 R 2 NH, wherein R 1 and R 2 are as above, in the appropriate organic solvent in the presence of alkali or R 1 R 2 for excess NH, and when R 5 and R 4 together with C (O) N form a ring of the formula: R C >.R C>. b6/ AuY kur R5 ir R6 yra H, Cx_4 alkilas arba halogenas,b 6 / AuY where R 5 and R 6 are H, C x 4 alkyl or halogen, b) (X) formulės junginį C\X XR2 kurioje A, B, D, E, R , aukščiau, o XI yra chloras, stadijoje, veikia šarmu tirpiklio ir vandens sistema, niniam katalizatoriui.b) Compound of formula (X) C 1 X X R 2 wherein A, B, D, E, R, above, and XI is chlorine, in the step of an alkali solvent-water system, for the catalyst. R ir R yra pažymėti bromas arba jodas, gautą a) arba dvifaze organinio dalyvaujant heteroge-R and R are labeled bromine or iodine derived from a) or biphasic organic in the presence of heterogene
LTIP578A 1989-02-02 1993-05-31 Method for the preparation of acylaminobenzamides derivatives LT3286B (en)

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Publication number Priority date Publication date Assignee Title
US4282218A (en) 1977-10-12 1981-08-04 Imperial Chemical Industries Limited Amides
EP0127990A2 (en) 1983-06-06 1984-12-12 Sumitomo Chemical Company, Limited Fungicidal aniline derivatives

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4282218A (en) 1977-10-12 1981-08-04 Imperial Chemical Industries Limited Amides
EP0127990A2 (en) 1983-06-06 1984-12-12 Sumitomo Chemical Company, Limited Fungicidal aniline derivatives

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