Народ, подкиньте методу синтеза тетроновой к-ты.
Посмотрев СОПы ИРЕА и т.д. увидел только методу на бромтетроновую к-ту со смешным выходом 35%.
Может есть какой нибудь более эффективный способ синтеза.
Синтез тетроновой к-ты
Задайте на www.scirus.com поиск с точной фразой preparation of tetronic acid.
Я сам не смотрел. Самый напрашивающийся ретросинтез - ацетол + диметилкарбонат или метил ортоформат.
Я сам не смотрел. Самый напрашивающийся ретросинтез - ацетол + диметилкарбонат или метил ортоформат.
Wodka trinkt man pur und kalt, das macht hundert Jahre alt!
Посмотрел ссылку - много всего, но ессно все БАВы и сложные производные, а надо то предшественник. Касаемо ретросинтеза, то еще проще через бромирование ацетоуксусного эфира, смещение брома к метильной группе и термическая циклизация. Но опять же подбирать условия для в-ва, синтезированного наверняка в 19 веке что ломает (да и бром с АУЭ жалко).Кстати на gallica.bnf.fr в старых подшивках тоже нету.
Bibliographic Information
New Synthesis of Tetronic Acid. (Preliminary Communication). Benary, Erich. I. Chem. Inst. Univ. Berlin, Ber. (1907), 40 1079-83. Journal language unavailable. CAN 1:6417 AN 1907:6417 CAPLUS
Abstract
Ethyl sodiomalonate (2 mol.) and chloracetyl chloride (1 mol.) yield, chiefly, ethyl tetronic-a-carboxylate, Et.O3CC CH2, which was identified by means of its barium salt. The mother liquor from the above ester contains another ester, C2H12O3, colorless needles, m. 91°-92°; mol. wt.=203. In aqueous solution it rapidly changes to the above tetronic acid derivative. Bromine produces the same change. Phenylhydrazide, C13H14O4N2, colorless, crystalline powder, m. and decomposes 188°-189°. Dry gaseous ammonia yields a compound, C7H6O4N, colorless, crystalline powder, m. and chars 243°. The hydroxamic acid, C6H7O3CONHOH, soft, colorless needles, m. and decomposes 180°. Ferric chloride gives a blue-violet color. Ammoniacal silver solution is reduced without heating. In a similar manner to the above synthesis bromisobutyryl bromide and ethyl sodiomalonate yield g,g-dimethyltetronic acid, CH2 , colorless plates m, 142°-143° with previous softening. It gives the characteristic red color with ferric chloride, and violet color with sodium nitrite, which are developed by tetronic acid.
Indexing -- Section 10 (Organic Chemistry)
Compound, C7H9O4N
Compound, C7H9O5N
Compound, C9H12O5
Tetronic acid, 3-carbethoxy-, phenylhydrazide
50630-62-1, Tetronic acid, 5,5-dimethyl-
(prepn. of)
4971-56-6, Tetronic acid
New Synthesis of Tetronic Acid. (Preliminary Communication). Benary, Erich. I. Chem. Inst. Univ. Berlin, Ber. (1907), 40 1079-83. Journal language unavailable. CAN 1:6417 AN 1907:6417 CAPLUS
Abstract
Ethyl sodiomalonate (2 mol.) and chloracetyl chloride (1 mol.) yield, chiefly, ethyl tetronic-a-carboxylate, Et.O3CC CH2, which was identified by means of its barium salt. The mother liquor from the above ester contains another ester, C2H12O3, colorless needles, m. 91°-92°; mol. wt.=203. In aqueous solution it rapidly changes to the above tetronic acid derivative. Bromine produces the same change. Phenylhydrazide, C13H14O4N2, colorless, crystalline powder, m. and decomposes 188°-189°. Dry gaseous ammonia yields a compound, C7H6O4N, colorless, crystalline powder, m. and chars 243°. The hydroxamic acid, C6H7O3CONHOH, soft, colorless needles, m. and decomposes 180°. Ferric chloride gives a blue-violet color. Ammoniacal silver solution is reduced without heating. In a similar manner to the above synthesis bromisobutyryl bromide and ethyl sodiomalonate yield g,g-dimethyltetronic acid, CH2 , colorless plates m, 142°-143° with previous softening. It gives the characteristic red color with ferric chloride, and violet color with sodium nitrite, which are developed by tetronic acid.
Indexing -- Section 10 (Organic Chemistry)
Compound, C7H9O4N
Compound, C7H9O5N
Compound, C9H12O5
Tetronic acid, 3-carbethoxy-, phenylhydrazide
50630-62-1, Tetronic acid, 5,5-dimethyl-
(prepn. of)
4971-56-6, Tetronic acid
Bibliographic Information
New Synthesis of Tetronic Acid. (Preliminary Communication). Benary, Erich. I. Chem. Inst. Univ. Berlin, Ber. (1907), 40 1079-83. Journal language unavailable. CAN 1:6417 AN 1907:6417 CAPLUS
Abstract
Ethyl sodiomalonate (2 mol.) and chloracetyl chloride (1 mol.) yield, chiefly, ethyl tetronic--carboxylate, Et.O3CC CH2, which was identified by means of its barium salt. The mother liquor from the above ester contains another ester, C2H12O3, colorless needles, m. 91-92; mol. wt.=203. In aqueous solution it rapidly changes to the above tetronic acid derivative. Bromine produces the same change. Phenylhydrazide, C13H14O4N2, colorless, crystalline powder, m. and decomposes 188-189. Dry gaseous ammonia yields a compound, C7H6O4N, colorless, crystalline powder, m. and chars 243. The hydroxamic acid, C6H7O3CONHOH, soft, colorless needles, m. and decomposes 180. Ferric chloride gives a blue-violet color. Ammoniacal silver solution is reduced without heating. In a similar manner to the above synthesis bromisobutyryl bromide and ethyl sodiomalonate yield ,-dimethyltetronic acid, CH2 , colorless plates m, 142-143 with previous softening. It gives the characteristic red color with ferric chloride, and violet color with sodium nitrite, which are developed by tetronic acid.
Indexing -- Section 10 (Organic Chemistry)
Compound, C7H9O4N
Compound, C7H9O5N
Compound, C9H12O5
Tetronic acid, 3-carbethoxy-, phenylhydrazide
50630-62-1, Tetronic acid, 5,5-dimethyl-
(prepn. of)
4971-56-6, Tetronic acid
Bibliographic Information
Preparation of tetronic acid. Neilands, L.; Neilands, O.; Vanags, G. (1964), SU 164298 19640813 Patent language unavailable. Application: SU 19630717. CAN 61:92030 AN 1964:492030 CAPLUS
Patent Family Information
Patent No. Kind Date Application No. Date
SU 164298 19640813 SU 19630717
Abstract
Tetronic acid is prepd. from the action of a 2-3N KOH soln. on -bromoacetoacetic ester at 10-25.
Bibliographic Information
Tetronic acid. Boosen, Karl J. (Lonza Ltd.). U.S. (1973), 2 pp. CODEN: USXXAM US 3758515 19730911 Patent written in English. Application: US 70-40699 19700526. Priority: . CAN 79:126297 AN 1973:526297 CAPLUS
Patent Family Information
Patent No. Kind Date Application No. Date
US 3758515 A 19730911 US 1970-40699 19700526
US 28242 E 19741112 US 1974-441028 19740207
Priority Application
CH 1969-8076 A 19690528
US 1970-40699 A 19700526
Abstract
ClCH2COCH2CO2Et and PhNH2 was refluxed in benzene for 3 hr to give -anilinocrotonic acid lactone. This was heated with 20% aq. NaOH for 12 hr and then acidified to give 60% of the title compd.
Patent Classifications
IPC: C07D. U.S.: 260343600.
Indexing -- Section 27-6 (Heterocyclic Compounds (One Hetero Atom)
Bibliographic Information
Tetronic acid. Mutulis, F.; Neilands, L.; Neilands, O. (Riga Polytechnical Institute, USSR). U.S.S.R. (1982), CODEN: URXXAF SU 792876 A1 19820130 Patent written in Russian. Application: SU 72-1852724 19721130. Priority: . CAN 97:23616 AN 1982:423616 CAPLUS
Patent Family Information
Patent No. Kind Date Application No. Date
SU 792876 A1 19820130 SU 1972-1852724 19721130
Priority Application
SU 1972-1852724 19721130
Abstract
The prepn. of tetronic acid was improved by acylating Na malonic esters with ClCH2COCl in the presence of solid CO2.
Bibliographic Information
Tetronic acid. Raimund, Miller; Leander, Tenud. (Lonza A.-G., Switz.). Eur. Pat. Appl. (1982), 8 pp. CODEN: EPXXDW EP 67408 A1 19821222 Designated States R: AT, BE, CH, DE, FR, GB, IT, LI, NL, SE. Patent written in German. Application: EP 82-105031 19820608. Priority: CH 81-3982 19810617. CAN 98:179198 AN 1983:179198 CAPLUS
Patent Family Information
Patent No. Kind Date Application No. Date
EP 67408 A1 19821222 EP 1982-105031 19820608
EP 67408 B1 19850327
R: AT, BE, CH, DE, FR, GB, IT, LI, NL, SE
CH 649996 A 19850628 CH 1981-3982 19810617
IL 65998 A1 19850228 IL 1982-65998 19820607
AT 12391 E 19850415 AT 1982-105031 19820608
US 4414400 A 19831108 US 1982-388432 19820614
SU 1220567 A3 19860323 SU 1982-3451243 19820615
JP 58000971 A2 19830106 JP 1982-103675 19820616
DD 202558 A5 19830921 DD 1982-240794 19820616
CA 1182830 A1 19850219 CA 1982-405284 19820616
HU 31158 O 19840428 HU 1982-1975 19820617
HU 186530 B 19850828
IN 155645 A 19850216 IN 1982-CA722 19820621
IN 156929 A 19851207 IN 1982-CA724 19820621
Priority Application
CH 1981-3982 A 19810617
EP 1982-105031 A 19820608
Abstract
Tetronic acid (I) was prepd. from 4-haloacetoacetate esters via 4-(tert-butoxy)acetoacetate esters. Treating NaH in THF with Me3COH at 40, then with ClCH2COCH2CO2Et in THF at room temp. gave 75.5% Me3COCH2COCH2CO2Et, which was treated with 18% HCl 6 h at room temp. to give 100% yield of 99.1% I.
Bibliographic Information
Tetronic acid. Miller, Raimund; Tenud, Leander. (Lonza A.-G., Switz.). Eur. Pat. Appl. (1982), 9 pp. CODEN: EPXXDW EP 67409 A1 19821222 Designated States R: AT, BE, CH, DE, FR, GB, IT, LI, NL, SE. Patent written in German. Application: EP 82-105032 19820608. Priority: CH 81-3983 19810617. CAN 98:215472 AN 1983:215472 CAPLUS
Patent Family Information
Patent No. Kind Date Application No. Date
EP 67409 A1 19821222 EP 1982-105032 19820608
EP 67409 B1 19850918
R: AT, BE, CH, DE, FR, GB, IT, LI, NL, SE
CH 649294 A 19850515 CH 1981-3983 19810617
IL 65999 A1 19850228 IL 1982-65999 19820607
AT 15670 E 19851015 AT 1982-105032 19820608
US 4421922 A 19831220 US 1982-388431 19820614
SU 1181536 A3 19850923 SU 1982-3450448 19820615
JP 58000972 A2 19830106 JP 1982-103676 19820616
DD 202153 A5 19830831 DD 1982-240791 19820616
CA 1182831 A1 19850219 CA 1982-405296 19820616
HU 31157 O 19840428 HU 1982-1972 19820617
HU 186528 B 19850828
Priority Application
CH 1981-3983 A 19810617
EP 1982-105032 A 19820608
Abstract
Tetronic acid (I) was prepd. from 4-haloacetoacetate esters via 4-(benzyloxy)acetoacetate esters. Treating NaH in THF with PhCH2OH at 40 and the product PhCH2ONa with ClCH2COCH2CO2Et in THF at 40 gave 83.2% PhCH2OCH2COCH2CO2Et, hydrogenolysis of which gave HOCH2COCH2CO2Et. This was cyclized to 95.8% pure tetronic acid, with an overall yield of 79.7% based on ClCH2COCH2CO2Et, 95.8% based on PhCH2OCH2COCH2CO2Et.
Bibliographic Information
Tetronic acid. Meul, Thomas; Tenud, Leander; Huwiler, Alfred. (Lonza A.-G., Switz.). Eur. Pat. Appl. (1985), 11 pp. CODEN: EPXXDW EP 153615 A1 19850904 Designated States R: AT, BE, CH, DE, FR, GB, IT, LI, NL, SE. Patent written in German. Application: EP 85-101150 19850204. Priority: CH 84-604 19840209. CAN 104:148723 AN 1986:148723 CAPLUS
Patent Family Information
Patent No. Kind Date Application No. Date
EP 153615 A1 19850904 EP 1985-101150 19850204
EP 153615 B1 19890426
R: AT, BE, CH, DE, FR, GB, IT, LI, NL, SE
CH 658056 A 19861015 CH 1984-604 19840209
HU 39441 A2 19860929 HU 1985-132 19850114
HU 196066 B 19880928
DD 229126 A5 19851030 DD 1985-272648 19850118
IN 162567 A 19880611 IN 1985-MA52 19850122
IL 74131 A1 19881130 IL 1985-74131 19850122
AT 42550 E 19890515 AT 1985-101150 19850204
CA 1225094 A1 19870804 CA 1985-473780 19850207
JP 60184073 A2 19850919 JP 1985-23386 19850208
JP 61056232 B4 19861201
SU 1436868 A3 19881107 SU 1985-3853848 19850208
Priority Application
CH 1984-604 A 19840209
EP 1985-101150 A 19850204
Abstract
4-Chloroacetoacetic ester was chlorinated to the 2,4-dichloroacetoacetic ester which, on thermolysis at 110-160 gave 3-chlorotetronic acid. Hydrogenolysis in the presence of a Pt metal catalyst gave tetronic acid. ClCH2COCH2CO2Et in CH2Cl2 was treated with SO2Cl2 .apprx.10 h at room temp. to give 96.1% pure ClCH2COCHClCO2Et which was refluxed 2.5 h at 140 to give 68.4% 3-chlorotetronic acid. Hydrogenolysis in H2O over 5% Pd/C gave tetronic acid in 65.6% overall yield.
думаю хватит
New Synthesis of Tetronic Acid. (Preliminary Communication). Benary, Erich. I. Chem. Inst. Univ. Berlin, Ber. (1907), 40 1079-83. Journal language unavailable. CAN 1:6417 AN 1907:6417 CAPLUS
Abstract
Ethyl sodiomalonate (2 mol.) and chloracetyl chloride (1 mol.) yield, chiefly, ethyl tetronic--carboxylate, Et.O3CC CH2, which was identified by means of its barium salt. The mother liquor from the above ester contains another ester, C2H12O3, colorless needles, m. 91-92; mol. wt.=203. In aqueous solution it rapidly changes to the above tetronic acid derivative. Bromine produces the same change. Phenylhydrazide, C13H14O4N2, colorless, crystalline powder, m. and decomposes 188-189. Dry gaseous ammonia yields a compound, C7H6O4N, colorless, crystalline powder, m. and chars 243. The hydroxamic acid, C6H7O3CONHOH, soft, colorless needles, m. and decomposes 180. Ferric chloride gives a blue-violet color. Ammoniacal silver solution is reduced without heating. In a similar manner to the above synthesis bromisobutyryl bromide and ethyl sodiomalonate yield ,-dimethyltetronic acid, CH2 , colorless plates m, 142-143 with previous softening. It gives the characteristic red color with ferric chloride, and violet color with sodium nitrite, which are developed by tetronic acid.
Indexing -- Section 10 (Organic Chemistry)
Compound, C7H9O4N
Compound, C7H9O5N
Compound, C9H12O5
Tetronic acid, 3-carbethoxy-, phenylhydrazide
50630-62-1, Tetronic acid, 5,5-dimethyl-
(prepn. of)
4971-56-6, Tetronic acid
Bibliographic Information
Preparation of tetronic acid. Neilands, L.; Neilands, O.; Vanags, G. (1964), SU 164298 19640813 Patent language unavailable. Application: SU 19630717. CAN 61:92030 AN 1964:492030 CAPLUS
Patent Family Information
Patent No. Kind Date Application No. Date
SU 164298 19640813 SU 19630717
Abstract
Tetronic acid is prepd. from the action of a 2-3N KOH soln. on -bromoacetoacetic ester at 10-25.
Bibliographic Information
Tetronic acid. Boosen, Karl J. (Lonza Ltd.). U.S. (1973), 2 pp. CODEN: USXXAM US 3758515 19730911 Patent written in English. Application: US 70-40699 19700526. Priority: . CAN 79:126297 AN 1973:526297 CAPLUS
Patent Family Information
Patent No. Kind Date Application No. Date
US 3758515 A 19730911 US 1970-40699 19700526
US 28242 E 19741112 US 1974-441028 19740207
Priority Application
CH 1969-8076 A 19690528
US 1970-40699 A 19700526
Abstract
ClCH2COCH2CO2Et and PhNH2 was refluxed in benzene for 3 hr to give -anilinocrotonic acid lactone. This was heated with 20% aq. NaOH for 12 hr and then acidified to give 60% of the title compd.
Patent Classifications
IPC: C07D. U.S.: 260343600.
Indexing -- Section 27-6 (Heterocyclic Compounds (One Hetero Atom)
Bibliographic Information
Tetronic acid. Mutulis, F.; Neilands, L.; Neilands, O. (Riga Polytechnical Institute, USSR). U.S.S.R. (1982), CODEN: URXXAF SU 792876 A1 19820130 Patent written in Russian. Application: SU 72-1852724 19721130. Priority: . CAN 97:23616 AN 1982:423616 CAPLUS
Patent Family Information
Patent No. Kind Date Application No. Date
SU 792876 A1 19820130 SU 1972-1852724 19721130
Priority Application
SU 1972-1852724 19721130
Abstract
The prepn. of tetronic acid was improved by acylating Na malonic esters with ClCH2COCl in the presence of solid CO2.
Bibliographic Information
Tetronic acid. Raimund, Miller; Leander, Tenud. (Lonza A.-G., Switz.). Eur. Pat. Appl. (1982), 8 pp. CODEN: EPXXDW EP 67408 A1 19821222 Designated States R: AT, BE, CH, DE, FR, GB, IT, LI, NL, SE. Patent written in German. Application: EP 82-105031 19820608. Priority: CH 81-3982 19810617. CAN 98:179198 AN 1983:179198 CAPLUS
Patent Family Information
Patent No. Kind Date Application No. Date
EP 67408 A1 19821222 EP 1982-105031 19820608
EP 67408 B1 19850327
R: AT, BE, CH, DE, FR, GB, IT, LI, NL, SE
CH 649996 A 19850628 CH 1981-3982 19810617
IL 65998 A1 19850228 IL 1982-65998 19820607
AT 12391 E 19850415 AT 1982-105031 19820608
US 4414400 A 19831108 US 1982-388432 19820614
SU 1220567 A3 19860323 SU 1982-3451243 19820615
JP 58000971 A2 19830106 JP 1982-103675 19820616
DD 202558 A5 19830921 DD 1982-240794 19820616
CA 1182830 A1 19850219 CA 1982-405284 19820616
HU 31158 O 19840428 HU 1982-1975 19820617
HU 186530 B 19850828
IN 155645 A 19850216 IN 1982-CA722 19820621
IN 156929 A 19851207 IN 1982-CA724 19820621
Priority Application
CH 1981-3982 A 19810617
EP 1982-105031 A 19820608
Abstract
Tetronic acid (I) was prepd. from 4-haloacetoacetate esters via 4-(tert-butoxy)acetoacetate esters. Treating NaH in THF with Me3COH at 40, then with ClCH2COCH2CO2Et in THF at room temp. gave 75.5% Me3COCH2COCH2CO2Et, which was treated with 18% HCl 6 h at room temp. to give 100% yield of 99.1% I.
Bibliographic Information
Tetronic acid. Miller, Raimund; Tenud, Leander. (Lonza A.-G., Switz.). Eur. Pat. Appl. (1982), 9 pp. CODEN: EPXXDW EP 67409 A1 19821222 Designated States R: AT, BE, CH, DE, FR, GB, IT, LI, NL, SE. Patent written in German. Application: EP 82-105032 19820608. Priority: CH 81-3983 19810617. CAN 98:215472 AN 1983:215472 CAPLUS
Patent Family Information
Patent No. Kind Date Application No. Date
EP 67409 A1 19821222 EP 1982-105032 19820608
EP 67409 B1 19850918
R: AT, BE, CH, DE, FR, GB, IT, LI, NL, SE
CH 649294 A 19850515 CH 1981-3983 19810617
IL 65999 A1 19850228 IL 1982-65999 19820607
AT 15670 E 19851015 AT 1982-105032 19820608
US 4421922 A 19831220 US 1982-388431 19820614
SU 1181536 A3 19850923 SU 1982-3450448 19820615
JP 58000972 A2 19830106 JP 1982-103676 19820616
DD 202153 A5 19830831 DD 1982-240791 19820616
CA 1182831 A1 19850219 CA 1982-405296 19820616
HU 31157 O 19840428 HU 1982-1972 19820617
HU 186528 B 19850828
Priority Application
CH 1981-3983 A 19810617
EP 1982-105032 A 19820608
Abstract
Tetronic acid (I) was prepd. from 4-haloacetoacetate esters via 4-(benzyloxy)acetoacetate esters. Treating NaH in THF with PhCH2OH at 40 and the product PhCH2ONa with ClCH2COCH2CO2Et in THF at 40 gave 83.2% PhCH2OCH2COCH2CO2Et, hydrogenolysis of which gave HOCH2COCH2CO2Et. This was cyclized to 95.8% pure tetronic acid, with an overall yield of 79.7% based on ClCH2COCH2CO2Et, 95.8% based on PhCH2OCH2COCH2CO2Et.
Bibliographic Information
Tetronic acid. Meul, Thomas; Tenud, Leander; Huwiler, Alfred. (Lonza A.-G., Switz.). Eur. Pat. Appl. (1985), 11 pp. CODEN: EPXXDW EP 153615 A1 19850904 Designated States R: AT, BE, CH, DE, FR, GB, IT, LI, NL, SE. Patent written in German. Application: EP 85-101150 19850204. Priority: CH 84-604 19840209. CAN 104:148723 AN 1986:148723 CAPLUS
Patent Family Information
Patent No. Kind Date Application No. Date
EP 153615 A1 19850904 EP 1985-101150 19850204
EP 153615 B1 19890426
R: AT, BE, CH, DE, FR, GB, IT, LI, NL, SE
CH 658056 A 19861015 CH 1984-604 19840209
HU 39441 A2 19860929 HU 1985-132 19850114
HU 196066 B 19880928
DD 229126 A5 19851030 DD 1985-272648 19850118
IN 162567 A 19880611 IN 1985-MA52 19850122
IL 74131 A1 19881130 IL 1985-74131 19850122
AT 42550 E 19890515 AT 1985-101150 19850204
CA 1225094 A1 19870804 CA 1985-473780 19850207
JP 60184073 A2 19850919 JP 1985-23386 19850208
JP 61056232 B4 19861201
SU 1436868 A3 19881107 SU 1985-3853848 19850208
Priority Application
CH 1984-604 A 19840209
EP 1985-101150 A 19850204
Abstract
4-Chloroacetoacetic ester was chlorinated to the 2,4-dichloroacetoacetic ester which, on thermolysis at 110-160 gave 3-chlorotetronic acid. Hydrogenolysis in the presence of a Pt metal catalyst gave tetronic acid. ClCH2COCH2CO2Et in CH2Cl2 was treated with SO2Cl2 .apprx.10 h at room temp. to give 96.1% pure ClCH2COCHClCO2Et which was refluxed 2.5 h at 140 to give 68.4% 3-chlorotetronic acid. Hydrogenolysis in H2O over 5% Pd/C gave tetronic acid in 65.6% overall yield.
думаю хватит
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