CN1095461C - Synthetic method for trifluoroacetyl acetophenone oxine and its derivative - Google Patents

Synthetic method for trifluoroacetyl acetophenone oxine and its derivative Download PDF

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CN1095461C
CN1095461C CN99113670A CN99113670A CN1095461C CN 1095461 C CN1095461 C CN 1095461C CN 99113670 A CN99113670 A CN 99113670A CN 99113670 A CN99113670 A CN 99113670A CN 1095461 C CN1095461 C CN 1095461C
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trifluoroacetyl
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acetophenone
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oxine
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姜标
张小兵
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Shanghai Institute of Organic Chemistry of CAS
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Abstract

The present invention relates to a synthetic method of trifluoroacetyl acetophenone oxime and a derivative thereof, and in the method, at the room temperature of 0 DEG C, arylamine, substituted arylamine, hybrid arylamine or substituted hybrid arylamine reacts with sodium nitrite under the condition of the existence of excessive inorganic acid for 0.1 to 1 hour to produce a diazo compound; the diazo compound reacts with trifluoroacetyl oxime in polar solvent by the catalytic reaction of inorganic copper or zinc compounds for 0.1 to 2 hours to produce the target products. The method has the advantages of simple operation and easy raw material obtainment, and is suitable for industrial production.

Description

The synthetic method of trifluoroacetyl acetophenone oxine and derivative thereof
The present invention relates to the synthetic method of a kind of trifluoroacetyl acetophenone oxine and derivative thereof, be by arylamine or assorted arylamine through diazotization after under the inorganic salt catalysis, promptly obtain trifluoroacetyl acetophenone oxine and derivative thereof with the reaction of trifluoro ethylidenehydroxylamine.
Trifluoroacetyl benzoylformaldoxime or trifluoroacetyl group substituted acetophenone and derivative thereof are intermediates important in the organic synthesis; especially trifluoromethyl is introduced in special applications in medicine, agricultural chemicals and the bioactive molecules; more widened the application prospect of this compounds; in AIDS medicine DMP266 (claiming Efavirenz again) synthetic; adopt following method synthetic intermediate (J.Org.Chem.; 44 (7), 1133,1979): Butyllithium is adopted in this reaction, and the preparation of butyllithium is difficult, and dangerous big, and reaction needed is synthetic under anaerobic and low temperature, and is also high to equipment requirements.
Trifluoroacetophenone synthesizes (Tetrahedron, 47,3207,1991) with methods such as paying a gram acylations, organometallics reagent usually, but all has many defectives.As pay a gram acylation reaction with acetylation reagent; mainly contain trifluoroacetyl chloride, trifluoroacetic anhydride (TFAA), trifluoracetic acid and trifluoromethanesulfonic acid and mix acetylation reagents such as acid anhydride, (2-trifluoroacetyl oxygen base) pyridine; wherein there is certain difficulty in trifluoroacetyl chloride on operation; though the two kinds of effects in back are good; but not too worthwhile economically, so trifluoroacetic anhydride (TFAA) commonly used:
Figure C9911367000032
But this class reaction generally needs the activatory aromatic ring could obtain better productive rate, and easily generates many acylations product and other by product, because the orientation effect of this reaction is difficult to the compound of synthetic special replacement, moreover reaction needs strictness to dewater.With organometallic reagent synthetic method, do not paid attention to for a long time owing to selectivity by people, give birth to
Figure C9911367000041
The product that becomes is easily continued attack and generates tertiary alcohol compound by organometallic reagent.Along with metal-organic development; can be with transition metal-catalyzed preparations such as palladium this class ketone or oxime; having overcome the orientation effect of Fu Yike reaction and the shortcoming of many acylations, but still be difficult to industrialization, mainly is many zincons; tin reagent; Tong Shijis etc. all are to be transformed by lithium reagent or Grignard reagent, and lithium reagent will run into the reaction of reactive hydrogen on the aromatic ring, in fact also are to have location selection problem; Grignard reagent is got by fragrant stew in soy sauce usually, and self a coupling side reaction is also arranged.In addition; no matter lithium reagent or Grignard reagent all need anhydrous and oxygen-free operation strictly in the preparation; cause continuous post-reacted strict control firing and explosion prevention; moreover transition metal reagent catalyzed reaction also needs the anhydrous and oxygen-free condition; substituting group has strict restriction on the reactant aromatic ring; as the hydroxyl on the need protection aromatic ring, amino etc., above-mentioned synthetic method is subjected to certain restriction.Once reported except that carbon-to-carbon double bond, diazonium salt can react (Organic Reaction, 24,225,1976) at copper catalysis and indivedual carbon-to-nitrogen double bon ethylidenehydroxylamines:
Figure C9911367000042
But do not reported with synthetic trifluoroacetyl group ketoxime of this method and trifluoroacetyl group substituted acetophenone oxime.So people still expect to solve the simple synthesis of trifluoroacetyl acetophenone oxine and trifluoroacetyl group substituted acetophenone oxime.
The purpose of this invention is to provide a kind of trifluoroacetophenone oxime and derivative simple synthesis thereof, say so further arylamine, substituted aromatic amines, assorted arylamine or replace assorted arylamine and nitrite under acidic conditions diazotization reaction takes place react under inorganic salt catalysis with the trifluoro ethylidenehydroxylamine to make trifluoroacetophenone oxime and derivative thereof then.
Synthetic method of the present invention can be represented with following formula:
Figure C9911367000043
In the above-mentioned reaction formula, R=aryl, substituted aryl, heteroaryl or substituted heteroaryl, aryl= Or
Figure C9911367000045
Substituted aryl=
Figure C9911367000046
Heteroaryl=
Figure C9911367000047
R 1, R 2, R 3Or R 4=H, X, OH, NO 2, NH 2, C 6H 4X, R 5Or OR 6, X=F, Cl, Br or I, R 5Or R 6=C 1-4Alkyl, HY is a mineral acid, Y=Cl, Br, NO 3Or HSO 4, described inorganic salt catalyst is inorganic copper compound, as copper sulfate CuSO 4, cupric chloride CuCl 2, and their hydrate, CuSO 45H 2O, CuSO 42H 2O, CuCl 22H 2O etc.
In the method for the invention, above-mentioned amine compound and Sodium Nitrite react in the presence of excessive mineral acid and generate diazonium compound RH 2 +Y -, temperature of reaction be 0 ℃ to room temperature, reaction times 0.1-1 hour, the mol ratio of described amine compound, Sodium Nitrite and mineral acid was 1: 1-3: 2-5.Adopt bigger mol ratio little to the product influence.
Diazonium compound and trifluoro ethylidenehydroxylamine react under described inorganic salt catalysis and generate trifluoroacetyl acetophenone oxine and derivative thereof
Figure C9911367000051
, R is ditto described.Diazonium compound, trifluoro ethylidenehydroxylamine and inorganic salt catalyst mol ratio are 1: 1-5: 0.1-1, temperature of reaction be 0 ℃ to room temperature, reaction times 0.1-2 hour.Add buffer reagent and will help improving productive rate in this reaction, adopt sodium-acetate to make buffer reagent usually, the mol ratio of diazonium compound and sodium-acetate is 1: 1-5.
In above-mentioned two reactions, because reaction is fierce, temperature of reaction control is on the low side for well.
In above-mentioned two reactions, adopt one or more polar solvents to help reaction usually and carry out, described polar solvent can be water, acetone, acetonitrile, dimethyl sulfoxide (DMSO), trichloroethane etc.
Adopt synthetic trifluoroacetyl acetophenone oxine of method of the present invention or trifluoroacetyl group substituted acetophenone oxime, not only react easy, raw material is easy to get, easy to operate, and be a kind of method that industrialization generates that is suitable for.
The present invention will be helped to understand by following embodiment, but content of the present invention can not be limited.
Synthesizing of embodiment 1 trifluoroacetyl benzoylformaldoxime and the single-substituted ethyl ketone of trifluoroacetyl group
The 0.68ml concentrated hydrochloric acid is mixed with 1.0ml water, add the 3mmol arylamine and be stirred to dissolving and be cooled to 0-10 ℃, slowly drip the solution of 3mmol Sodium Nitrite in 0.4m1 water.Adding the back stirred 10-20 minute under this temperature.In another reaction flask, add 15mmol trifluoro ethylidenehydroxylamine and water 2ml, the 1mmol Salzburg vitriol, the 16.5mmol sodium-acetate is cooled to 0 ℃ under stirring.Above-mentioned diazonium salt solution slowly is added drop-wise to wherein.Add the back 10-15 ℃ of reaction half an hour, add water 20ml, with ether 3 * 25ml extraction.Merge organic layer, respectively with after saturated sodium bicarbonate and the salt solution washing, anhydrous sodium sulfate drying.Steaming desolventizes back column chromatography (ethyl acetate: sherwood oil=1: 9) get pure product.List in the table 1.
Table 1
Figure C9911367000061
Compound 1IR, cm -1: 3292,1719,1674,1601,1462,1444,1338cm -1 1HNMR, δ: 7.43 (s, 5H), 9.10 (s, 1H) 19FNMR, δ :-11.2 (s) MS, m/e:189 (M +) C 8H 6F 3NO calculated value: C 50.79, H 3.17, and N 7.41189.13 measured value: C 50.45, and H 3.19, N 7.38 compound 2IR, cm -1: 3392,2880,1621,1535,1353,1197,976,723 1HNMR, δ: 7.6～8.0 (m, 2H), 8.2～8.5 (m, 1H), 9.8 (s, 1H) 19FNMR, δ :-11.0 (s) MS, m/e:234 (M +) C 8H 5F 3N 2O 3Calculated value: C 41.04, H 2.15, and N 11.96234.13 measured value: C 41.02, and H 2.14, N 11.99 compound 3IR, cm -1: 3447,3112,2871,2458,1944,1605,1522,1355,9721HNMR, δ: 7.7 (d, 2H), 8.3 (d, 2H), 9.1 (s, 1H) 19FNMR, δ :-11.0 (s) MS, m/e:234 (M +) C 8H 5F 3N 2O 2Calculated value: C 41.04, H 2.15, and N 11.96234.13 measured value: C 41.01, and H 2.16, N 12.01 compound 4IR, cm -1: 3256,1612,1574,1518,1461,1415,1267 1HNMR, δ: 3.90 (s, 3H), 7.0 (d, 2H, J=10Hz), 7.62 (d, 2H, J=10Hz), 9.70 (s, 1H) 19FNMR, δ :-11.6 (s) MS, m/e:219 (M +), 204 (M +-CH 3) C 9H 8F 3NO 2Calculated value: C 49.32, H 3.68, and N 6.39219.26 measured value: C 49.37, and H 3.65, N 6.34 compound 5IR, cm -1: 3294,2928,1914,1612,1571,1457,1297,964 1HNMR, δ: 2.4 (s, 3H), 7.2～7.5 (dd, 4H, J 1=3Hz, J 2=7Hz), 9.12 (s, 1H) 19FNMR, δ :-10.8 (s) MS, m/e:203 (M +) C 9H 8F 3NO calculated value: C 53.20, H 3.96, and N 6.89203.16 measured value: C 53.15, and H 3.98, N 6.91 compound 6IR, cm -1: 3325,3083,2426,1597,1569,1477,1339,787 1HNMR, δ: 7.4～7.6 (m, 4H), 9.43 (s, 1H) 19FNMR, δ :-11.7 (s) MS, m/e:223 (M +), 188 (M +-Cl) C 8H 5F 3NOCl calculated value: C 42.98, H 2.25, and N 6.26223.57 measured value: C 42.84, and H 2.21, N 6.29 compound 7IR, cm -1: 3328,3103,2925,1621,1340,765,733 1HNMR, δ: 7.3～7.5 (dd, 4H, J 1=2Hz, J 2=6Hz), 9.2 (s, 1H) 19FNMR, δ: 268 (M +), 189 (M +-Br) C 8H 5BrF 3NO calculated value: C 35.85, H 1.88, and N 5.22
Measured value: C 35.87, H 1.85 N 5.20 compound 8IR, cm -1: 3450,2128,3100,1624,1205,1109,732 1HNMR, δ: 4.2 (broad, 1H), 6.8～7.1 (dd, 4H, J 1=5Hz, J 2=12Hz), 9.6 (s, 1H) 19FNMR, δ :-11.8 (s) MS, m/e:205 (M +) C 8H 6F 3NO 2Calculated value: C 46.84, H 2.95, and N 6.83205.13 measured value: C 46.84, and H 2.93, N 6.79 compound 9IR, cm -1: 3378,3285,2917,2310,1617,1458,1109,986,71 1HNMR, δ: 2.10 (s, 6H), 6.7～7.05 (dd, 4H, J 1=4Hz, J 2=7Hz), 9.2 (s, 1H) 19FNMR, δ :-11.1 (s) MS, m/e:232 (M +) C 10H 11F 3N 2O calculated value: C 51.73, H 4.77, and N 12.06232.20 measured value: C 51.76, and H 4.75, N 12.07 compound 10IR, cm -1: 3323,3124,2235,1617,1187,976,801 1HNMR, δ: 7.25 (dd, J 1=7Hz, J 2=3Hz, 4H), 7.4 (dd, J 1=9Hz, J 2=2Hz, 4H), 9.1 (s, 1H) 19FNMR, δ :-11.0 ((s) MS, m/e:283 (M +) C 14H 9F 4NO calculated value: C 59.37, H 3.20, and N 4.94283.22 measured value: C 59.34, and H 3.21, N 4.90 compound 11IR, cm -1: 3325,3280,2708,2105,1658,1329,1109,820 1HNMR, δ: 7.2-7.5 (m, 3H), 7.8 (s, 1H), 9.3 (s, 1H) MS, m/e:257 (M +), 188 (M +-CF 3) C 9H 5F 6NO calculated value: C 42.04, H 1.96, and N 5.45257.13 measured value: C 42.01, and H 1.95, N 5.45 compound 12IR, cm -1: 3354,3109,2587,2271,1621,1320,1009,787 1HNMR, δ: 2.9 (broad, 1H), 7.2～7.5 (m, 4H), 9.7 (s, 1H) 19FNMR, δ :-11.0 (s, 3F) MS, m/e:221 (M +), 188 (M +-SH) C 8H 6F 3NO 3Calculated value: C 43.44, H 2.73, and N 6.33221.20 measured value: C 43.47, and H 2.70, and N 6.32
Embodiment 2
With 3-10 mole concentrated hydrochloric acid or sulfuric acid and the mixing of 0.5-1 premium on currency, drip 3 moles of arylamine, be chilled to 0-10 ℃ after the dissolving, add the mixed solution of 4 moles of Sodium Nitrites and 500ml water, finish and continue to stir 0.1-1 hour.Then this diazonium salt solution slowly is added drop-wise to 15 moles of trifluoro ethylidenehydroxylamines, 1 premium on currency, 0.5 liter of dimethyl methyl sulfone, 1 mole of cupric sulfate pentahydrate or cupric chloride.In the 16 molar acetate sodium solutions, behind the effusion bubble, continue to react 0.5 hour in the reaction, add 20 liters in water,, merge organic layer, use saturated NaHCO with 3 * 25 liters of extracted with diethyl ether in 5-20 ℃ 3Washed twice, salt is washed once, uses anhydrous sodium sulfate drying, steams to desolventize and obtains product.In result such as table 2 and the table 3.
Table 2
Sequence number R 1 R 2 R 3 R 4 Productive rate (%)
13 14 15 16 17 4-F 4-Cl 4-Cl 4-F 4-F 3-F 2-NO 2 2-F 3-F 3-F H H H 2-F 2-NO 2 H H H H H 62 43 54 41 40
Table 3 Compound 13IR, cm -1: 3430,3286,3090,1654,1389,1186,737 1HNMR, δ: 7.6～7.8 (m, 3H), 9.15 (s, 1H) 19FNMR, δ :-12.3 (s, 3F), 25.4 (m, 1F), 29.7 (m, 1F) MS, m/e:225 (M +) C 8H 4F 5NO calculated value: C 42.68, H 1.79, and N 6.22225.12 measured value: C 42.65, and H 1.81, N 6.23 compound 14IR, cm -1: 3325,3185,2820,1643,1341,769,758 1HNMR, δ: 7.6～8.1 (m, 3H), 9.4 (s, 1H) 19FNMR, δ :-11.0 (s) MS, m/e:254 (M +), 219 (M +-C1) C 8H 4ClF 3NO 3Calculated value: C 37.74, H 1.58, and N 5.50254.57 measured value: C 37.70, and H 1.59, N 5.47 compound 15IR, cm -1: 3364,3108,2920,2108,1635,1208,1104,780 1HNMR, δ: 7.2 (s, 1H), 7.4～7.7 (dd, J 1=8Hz, J 2=3Hz, 2H) 19FNMR, δ :-11.2 (s) MS, m/e:241 (M +), 206 (M +-Cl) C 8H 4ClF 4NO calculated value: C 39.78, H 1.67, and N 5.80241.57 measured value: C 39.79, and H 1.65, N 5.80 compound 16IR, cm -1: 3329,3230,2786,2415,1650,1379,1184,806 1HNMR, δ: 7.4～7.7 (m, 2H), 9.27 (s, 1H) 19FNMR, δ :-11.9 (s, 3F), 23.7 (dd, 1F), 25.1 (d, 1F), 28.5 (dd, 1F) MS, m/e:243 (M +) C 8H 3F 6NO calculated value: C 39.51, H 1.24, and N 5.76243.17 measured value: C 39.48, and H 1.26, N 5.75 compound 17IR, cm -1: 3343,3218,2717,1639,1370,910,819 1HNMR, δ: 7.4～7.65 (m, 2H), 9.3 (s, 1H) 19FNMR, δ :-11.7 (s, 3F), 23.9 (dd, 1F), 26.7 (d, 1F) MS, m/e:270 (M +), 224 (M +-NO 2) C 8H 3F 5N 2O 3Calculated value: C 35.57, H 1.12, and N 10.37270.11 measured value: C 35.53, and H 1.10, N 10.39 compound 18IR, cm -1: 3320,3031,2015,1627,1478,1190,715 1HNMR, δ: 7.1～7.6 (m, 7H), 9.2 (s, 1H) 19FNMR, δ :-11.5 (s, 3F) MS, m/e:239 (M +), 170 (M +-CF 3), C 12H 8F 3NO calculated value: C 60.26, H 3.37, and N 5.86239.19 measured value: C 60.23, and H 3.37, N 5.89 compound 19IR, cm -1: 3318,2928,2315,1671,1192,1078,892 1HNMR, δ: 7.51 (m, 3H), 8.3 (s, 1H), 9.8 (s, 1H) 19FNMR, δ :-11.1 (s) MS, m/e:190 (M +) C 7H 5F 3N 2O calculated value: C 44.22, H 2.65, and N 14.73190.12 measured value: C 44.22, and H 2.64, N 14.76 compound 20IR, cm -1: 3341,3105,2725,1619,1098,925,746 1HNMR, δ: 7.4～8.5 (m, 6H), 9.7 (s, 1H) 19FNMR, δ :-10.8 (s) MS, m/e:216 (M +), 147 (M +-CF 3) C 9H 7F 3N 2O calculated value: C 50.01, H 3.26, and N 12.96216.16 measured value: C 50.04, and H 3.25, and N 12.99

Claims (6)

1. the synthetic method of trifluoroacetyl acetophenone oxine and derivative thereof; comprise that arylamine, substituted aromatic amines, assorted arylamine or the assorted arylamine of replacement and Sodium Nitrite react the generation diazonium compound in the presence of excessive mineral acid; diazonium compound and alkyl ethylidenehydroxylamine in polar solvent through inorganic copper compound catalyzed reaction; it is characterized in that described alkyl ethylidenehydroxylamine is the trifluoro ethylidenehydroxylamine, described amine compound is RNH 2, R=wherein
Figure C9911367000022
Or , R 1, R 2, R 3Or R 4=H, X, OH, NO 2, NH 2, C 6H 4X, R 5Or OR 6, X=F, Cl, Br or I, R 5Or R 6=C 1-4Alkyl.
2. the synthetic method of trifluoroacetyl acetophenone oxine as claimed in claim 1 and derivative thereof, the mol ratio that it is characterized in that described amine, Sodium Nitrite and mineral acid is 1: 1-3: 2-5, temperature of reaction be 0 ℃ to room temperature, the reaction times is 0.1-1 hour.
3. the synthetic method of trifluoroacetyl acetophenone oxine as claimed in claim 1 and derivative thereof; it is characterized in that described diazonium compound and trifluoro ethylidenehydroxylamine react under inorganic copper compound catalysis; mol ratio is followed successively by 1: 1-5: 0.1-1; temperature of reaction is 0 a ℃-room temperature, reaction times 0.1-2 hour.
4. the synthetic method of trifluoroacetyl acetophenone oxine as claimed in claim 1 and derivative thereof; when it is characterized in that diazonium compound and trifluoro ethylidenehydroxylamine react under inorganic copper compound catalysis; also have the buffer reagent sodium-acetate, diazonium compound and sodium-acetate mol ratio are 1: 1-5.
5. the synthetic method of trifluoroacetyl acetophenone oxine as claimed in claim 4 and derivative thereof is characterized in that described inorganic copper compound is CuSO 4, CuSO 45H 2O, CuSO 42H 2O, CuCl 2Or CuCl 22H 2O.
6. the synthetic method of trifluoroacetyl acetophenone oxine as claimed in claim 4 and derivative thereof is characterized in that described polar solvent is one or more the polar solvent in water, acetone, acetonitrile, dimethyl sulfoxide (DMSO), the trichloroethane.
CN99113670A 1999-04-30 1999-04-30 Synthetic method for trifluoroacetyl acetophenone oxine and its derivative Expired - Fee Related CN1095461C (en)

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CN1083807A (en) * 1992-06-30 1994-03-16 Dsm有限公司 Oxime changes into the method for corresponding amides

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CN1083807A (en) * 1992-06-30 1994-03-16 Dsm有限公司 Oxime changes into the method for corresponding amides

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